JP2016021068A - Photosensitive resin composition, material for forming pattern, and pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition that can reduce a developing time and can give a good pattern shape.SOLUTION: The photosensitive resin composition comprises a polyimide precursor having a structure represented by formula (1) below and a photobase generator.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition, a pattern forming material, a pattern forming method, and an article formed at least in part by the photosensitive resin composition or a cured product thereof.

  In recent years, with the high integration and high reliability of semiconductor devices, high heat-resistant resin has attracted attention as a material used for interlayer insulation films such as circuit wiring, surface protection films, multichip modules, etc. Have been bathed. Among high heat resistance resins, polyimide resin is widely used because of its excellent heat resistance, mechanical properties, electrical properties such as low dielectric constant and high insulation, flattening ability, workability, etc. Yes.

  Polyimide is a polymer synthesized from diamine and acid dianhydride. By reacting diamine and acid dianhydride in a solution, it becomes polyamic acid (polyamic acid) which is a precursor of polyimide, and then becomes a polyimide through a dehydration ring closure reaction. In general, since polyimide has poor solubility in a solvent and is difficult to process, when pattern formation is performed on a polyimide material, it is necessary to form a photoresist pattern on the polyimide coating and then perform an etching process. Therefore, complication of the process is inevitable. Therefore, in many cases, a photosensitive polyimide composition having a pattern forming ability is used in the polyimide material itself.

  As a photosensitive polyimide composition, a system comprising a polyimide precursor and dichromate was first proposed (Patent Document 1). However, this material has advantages such as practical photosensitivity and high film-forming ability, but lacks storage stability and has the disadvantage that chromium ions remain in the cured polyimide resin. There was no practical use.

As another photosensitive polyimide material, a method of directly forming a pattern using a polyamic acid alkyl ester and a photobase generator (Patent Document 2), a method of directly forming a pattern using a polyamic acid and a photobase generator ( Patent Document 3) has been proposed. This technique is characterized in that a photosensitive polyimide can be prepared simply by mixing a polyimide precursor such as polyamic acid alkyl ester or polyamic acid and a photobase generator. It utilizes the fact that it acts as a catalyst that promotes the imidization reaction, and forms a pattern by generating a basic substance that is latent in the photobase generator by position-selection by exposure.
In the techniques disclosed in Patent Document 2 and Patent Document 3, a photosensitive resin composition is applied onto a substrate to form a coating film, and actinic rays of a photobase generator are irradiated through a photomask. Thereby, a base is generated only in the exposed portion. Next, when the coating film is subjected to heat treatment (PEB: Post Exposure Bake), imidization of the exposed area and the unexposed area of the exposed area is promoted by the catalytic action of the base as compared with the unexposed area. A difference in rate occurs. When the imidization ratio is different, the dissolution rate in the developer is also different, and thus the pattern of the insulating resin layer is obtained using the difference in the dissolution rate in the developer generated here. In general, the higher the imidization rate, the lower the solubility in organic solvents and basic aqueous solutions. In these methods, the imidation rate of the exposed area is larger than that of the unexposed area. The part dissolves in the developer, and the exposed part functions as a negative photosensitive material that remains as a pattern.
In the case of the technique of Patent Document 2, an organic solvent is used as a developer because the polyamic acid alkyl ester is insoluble in an aqueous solution. In addition, polyamic acid alkyl ester is characterized by excellent storage stability.
On the other hand, in the case of the technique of Patent Document 3, the polyamic acid has a carboxyl group in the skeleton, so it is soluble in an alkaline aqueous solution, a basic aqueous solution can be used as a developer, and the environmental load is small. Since the carboxyl group disappears in the course of the conversion, there is a feature that the rate of decrease in solubility in the basic aqueous solution is large, and the difference in solubility in the developer between the exposed portion and the unexposed portion can be further increased. In recent years, a study using a polyamic acid that can be developed with a basic aqueous solution has been actively conducted because of increasing interest in the environment and reducing the cost of waste liquid treatment.

Japanese Patent Publication No.49-17374 JP-A-5-197148 JP-A-8-227154

In the pattern formation method as described above, the remaining film ratio of the exposed portion (pattern film thickness after development / film thickness of the coating film before development: relative to the initial film thickness of the film remaining as a pattern without dissolving in the developer. In order to increase the ratio), it is necessary to increase the temperature of post-exposure heating in order to increase the imidization ratio of the exposed portion. At that time, imidization of the unexposed area proceeds in the same manner, so that the solubility of the unexposed area in the developer is lowered, and it becomes necessary to use a stronger developer with a higher concentration or safety. Even when a highly dilute basic aqueous solution can be used, there is a problem that the development time becomes long.
In the case of a photosensitive polyimide that uses a photobase generator, unlike the photosensitive polyimide that forms a pattern by other mechanisms, the unexposed area was coated with the photosensitive resin composition of the present invention during development. Since it changes from the state immediately after it (imidation progresses), improvement of the developability of an unexposed part attracts attention as an especially important subject.

  The present invention has been made in view of the above problems, and provides a photosensitive resin composition capable of shortening the development time during pattern formation and improving the pattern shape obtained. With the goal.

  As a result of repeated studies to solve the above problems, the present inventors have used a polyimide precursor that has been improved by making the structure of the terminal portion into a specific skeleton, thereby allowing an unexposed portion of the photosensitive resin composition to be used. The present inventors have obtained the knowledge that a good pattern shape can be obtained by increasing the dissolution rate, reducing the development time, and increasing the ratio of the dissolution rate between the unexposed area and the exposed area. It came to complete.

  That is, the photosensitive resin composition of the present invention is characterized by containing a polyimide precursor containing at least a structure represented by the following formula (1) and a photobase generator.

(In the formula (1), R ¹ is a tetravalent organic group, R ² is a divalent organic group, R ³ is a hydrogen atom or a monovalent organic group, R ⁴ is a hydrogen atom or the following formulas (2) to ( 5) is at least one organic group selected from the group consisting of organic groups, and at least a part of R ⁴ is an organic group, and a plurality of R ¹ , R ² , R ³ and R ⁴ are Each may be the same or different.)

(In Formula (2), R ⁵ is a tetravalent organic group, and R ⁶ is a hydrogen atom or a monovalent organic group.)

(In Formula (3), R ⁷ is a tetravalent organic group, R ⁸ is a hydrogen atom or a monovalent organic group. Plural R ^8s may be the same or different.)

(In Formula (4), R ⁹ is a tetravalent organic group, R ¹⁰ and R ¹¹ are a hydrogen atom or a monovalent organic group. Plural R ^10s may be the same or different.)

(In formula (5), X is a C, P or S atom, Y is an S or O atom, Z is —R ¹² or —OR ¹³ , and R ¹² and R ¹³ are monovalent organic groups.)

  X in the formula (5) is a carbon atom, and Y in the formula (5) is an oxygen atom, it is easy to obtain an end-capping agent that forms such a terminal, and It is preferable because it is easy to handle.

  Furthermore, when the formula (5) is an organic group represented by the following formula (6), when the polyimide precursor is imidized, the terminal site is also imidized, so that moisture is absorbed when it becomes a polyimide. This is preferable because the heat resistance is low and the heat resistance is high.

(In the formula (6), R ¹⁴ is an organic group selected from the group consisting of organic groups represented by the following formulas (6-1) to (6-5), and R ¹⁵ is a hydrogen atom or a monovalent organic group. is there.)

(In the formulas (6-1) to (6-5), A each independently represents a hydrogen atom or an organic group, which may be the same or different. (It may be bonded to form a cyclic structure and may contain a heteroatom bond. -COOR corresponds to -COOR ¹⁵ in formula (6).)

Of R ⁴ in the formula (1), 50% or more is preferably an organic group from the viewpoint of further shortening the development time, more preferably 70% or more is an organic group, and more preferably 90%. % Or more is more preferable, and 95% or more is most preferable.

Furthermore, it is preferable that 50% or more of R ⁴ in the above formula (1) has the organic group represented by the above formula (6) because the hygroscopic property is lower and the heat resistance is higher.

It is preferable from the two viewpoints (1) and (2) below that the photobase generator is at least one selected from the group consisting of compounds represented by the following formulas (7) to (9).
(1) Since it is easily decomposed or volatilized in the heating process performed after development, even if it is exposed to a high temperature atmosphere or vacuum atmosphere in the subsequent process, (2) By combining electromagnetic wave irradiation and heating, it is possible to efficiently generate a base with a small amount of electromagnetic wave irradiation, compared to conventional so-called photobase generators. And high sensitivity.

(In Formula (7), R ⁴¹ and R ⁴² each independently represent a hydrogen atom or an organic group, and may be the same or different. R ⁴¹ and R ⁴² are bonded to form a ring. It may form a structure and may contain a bond of hetero atoms, provided that at least one of R ⁴¹ and R ⁴² is an organic group, and R ⁴³ and R ⁴⁴ are each independently a hydrogen atom, A halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, or organic group, may be different even in the same ^{.R 45, R 46,} R ⁴⁷ and ^{R 48} are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, Sulf Group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group or organic group, which are the same. Two or more of R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ may be bonded to form a cyclic structure, and may contain a hetero atom bond. R ⁴⁹ is a hydrogen atom or a protecting group that can be deprotected by heating and / or irradiation with electromagnetic waves.)

(In Formula (8), R ⁴¹ and R ⁴² each independently represent a hydrogen atom or an organic group, and may be the same or different. R ⁴¹ and R ⁴² are bonded to form a ring. may form a structure, may contain a binding heteroatom. proviso that at least one of R ⁴¹ and R ⁴² is an organic group .R ⁵⁰ and R ^{50 'each} independently represents a hydrogen atom, A halogen atom, a hydroxyl group, a mercapto group, a nitro group, a silyl group, a silanol group, or an organic group, R ⁵¹ , R ⁵² , R ⁵³ , R ^54, and R ⁵⁵ are each independently a hydrogen atom, a halogen atom, or a hydroxyl group; , Mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group Amino group, an ammonio group or an organic group, may be different even in the same ^{.R 51, R 52, R 53} , R 54 and ^{R 55} are a ring structure bonded to two or more of them It may be formed or may contain a heteroatom bond.)

(In the formula (9), R ⁵⁷ is an amino group or an organic group substituted with an organic group, R ⁵⁸ and R ⁵⁹ are each independently a hydrogen atom, a halogen atom, a sulfide group, a silyl group, a silanol group, a nitro group, Group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, amino group, ammonio group or organic group, which may be the same or different, ^At least one of ⁵⁸ and R ^{59 is} an aromatic compound which may have a hetero atom, and two or more of R ⁵⁷ , R ⁵⁸ and R ⁵⁹ are bonded to form a cyclic structure. And may contain heteroatom bonds.)

  Furthermore, the present invention provides a pattern forming material comprising the photosensitive resin composition of the present invention.

  Moreover, the present invention forms a coating film or a molded body using the photosensitive resin composition of the present invention, and the coating film or molded body is irradiated with electromagnetic waves in a predetermined pattern, and heated after irradiation or simultaneously with irradiation. And providing a negative pattern forming method, wherein development is performed after changing the solubility of the irradiated portion.

  Furthermore, printed matter, paint, sealant, adhesive, display device, semiconductor device, electronic component, microelectromechanical system, stereolithography product, which is at least partially formed from the photosensitive resin composition of the present invention or a cured product thereof. Articles such as optical members or building materials are also provided.

According to the present invention, it is possible to provide a photosensitive resin composition having a short development time and a good pattern shape.
Furthermore, according to the present invention, an article having a good pattern shape can be provided.

It is a schematic diagram of the polyimide precursor by which the terminal is an amine. It is a schematic diagram which shows an example of the intermolecular interaction of the polyimide precursor by which the terminal is an amine.

The present invention will be described in detail below.
In the present invention, unless otherwise specified, the electromagnetic wave is not only an electromagnetic wave having a wavelength in the visible and invisible regions, but also a particle beam such as an electron beam, and radiation or a general term for the electromagnetic wave and the particle beam. Contains ionizing radiation. In this specification, irradiation with electromagnetic waves is also referred to as exposure. Note that electromagnetic waves with wavelengths of 365 nm, 405 nm, and 436 nm may be referred to as i-line, h-line, and g-line, respectively.
Moreover, in this invention, an organic group represents the general term of the functional group containing at least 1 carbon atom.

1. Photosensitive resin composition The photosensitive resin composition of this invention contains the polyimide precursor containing the structure represented by following formula (1) at least, and a photobase generator, It is characterized by the above-mentioned.

(In the formula (1), R ¹ is a tetravalent organic group, R ² is a divalent organic group, R ³ is a hydrogen atom or a monovalent organic group, R ⁴ is a hydrogen atom or the following formulas (2) to ( 5) is at least one organic group selected from the group consisting of organic groups, and at least a part of R ⁴ is an organic group, and a plurality of R ¹ , R ² , R ³ and R ⁴ are Each may be the same or different.)

(In Formula (2), R ⁵ is a tetravalent organic group, and R ⁶ is a hydrogen atom or a monovalent organic group.)

(In Formula (3), R ⁷ is a tetravalent organic group, R ⁸ is a hydrogen atom or a monovalent organic group. Plural R ^8s may be the same or different.)

(In Formula (4), R ⁹ is a tetravalent organic group, R ¹⁰ and R ¹¹ are a hydrogen atom or a monovalent organic group. Plural R ^10s may be the same or different.)

(In formula (5), X is a C, P or S atom, Y is an S or O atom, Z is —R ¹² or —OR ¹³ , and R ¹² and R ¹³ are monovalent organic groups.)

The photosensitive resin composition of the present invention is a negative photosensitive resin composition that requires post-exposure heating. Such a photosensitive resin composition promotes curing and insolubilizes by a thermal reaction using chemical species generated by exposure in an exposed portion.
The photosensitive resin composition of the present invention includes at least a photobase generator that generates a chemical species that acts as a catalyst upon exposure, and a polyimide precursor that promotes an imidization reaction by heating in the presence of the chemical species. It is.

The polyimide precursor of the present invention has a lower dissolution rate in a developing solution such as a basic aqueous solution due to imidization. In the exposed area, a base is generated from the photobase generator, which becomes a catalyst for promoting imidization of the polyimide precursor, and a difference occurs in the imidation ratio between the exposed and unexposed areas of the polyimide precursor.
Due to the difference in the imidization ratio of the polyimide precursor, the dissolution rate of the exposed portion with respect to the developer becomes lower than the dissolution rate of the unexposed portion, and a pattern is formed by the developing process.

In the present invention, as a polyimide precursor including the structure represented by the above formula (1), the use of the one having at least a part of the terminal as an organic group can exhibit an effect of shortening the development time. Although it is unclear, it is presumed as follows.
As shown in the schematic diagram of the polyimide precursor shown in FIG. 1, a plurality of carboxyl groups exist in the polyimide precursor molecule. When R ^{4 in the} above formula (1) is a hydrogen atom, the terminal is an amino group. In the coating film after drying, as schematically shown in FIG. 2, it is considered that most of the carboxyl group and the terminal amino group interact with each other to form a salt. For this reason, when amino groups are present at both ends of the molecular chain of the polyimide precursor, when the amino group interacts with a carboxyl group of a different molecular chain, the molecular chain functions in a pseudo-crosslinking manner. As a result, it is considered that the molecular weight becomes pseudo infinite, the polyimide precursor behaves like a gel (crosslinked body), and the dissolution rate in the developing solution becomes slow.
On the other hand, when at least a part of R ^{4 in} the formula (1) is an organic group, the number of polyimide precursors in the weakly bonded state decreases. As a result, the solubility in the developer is improved, so that the development time can be shortened. As the number of terminal amino groups of the polyimide precursor decreases, the apparent molecular weight decreases and the dissolution rate in the developer increases. In particular, when at least one end of one side of the molecular chain is not an amino group, other molecules do not cross-link between two different molecular chains, so that the development speed is increased.
Hereinafter, the component which comprises the photosensitive resin composition of this invention is demonstrated.

1-1. Polyimide precursor The polyimide precursor used for this invention has a structure represented by following formula (1).

(In the formula (1), R ¹ is a tetravalent organic group, R ² is a divalent organic group, R ³ is a hydrogen atom or a monovalent organic group, R ⁴ is a hydrogen atom or the following formulas (2) to ( 5) is at least one organic group selected from the group consisting of organic groups, and at least a part of R ⁴ is an organic group, and a plurality of R ¹ , R ² , R ³ and R ⁴ are Each may be the same or different.)

(In Formula (2), R ⁵ is a tetravalent organic group, and R ⁶ is a hydrogen atom or a monovalent organic group.)

(In Formula (3), R ⁷ is a tetravalent organic group, R ⁸ is a hydrogen atom or a monovalent organic group. Plural R ^8s may be the same or different.)

(In Formula (4), R ⁹ is a tetravalent organic group, R ¹⁰ and R ¹¹ are a hydrogen atom or a monovalent organic group. Plural R ^10s may be the same or different.)

(In formula (5), X is a C, P or S atom, Y is an S or O atom, Z is —R ¹² or —OR ¹³ , and R ¹² and R ¹³ are monovalent organic groups.)

Examples of the case where R ³ is a monovalent organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and C _n H _2n OC _m H _{2m + 1} containing an ether bond therein. The structure etc. can be mentioned.

As a polyimide precursor, it is preferable that at least one has a carboxyl group from the viewpoint of increasing the solubility in an alkali developer. Among them, in Formula (1), among R ³ , 30 mol% or more is preferably a hydrogen atom, more preferably 50 mol% or more, still more preferably 90 mol% or more, and substantially A polyamic acid in which all of R ³ are hydrogen atoms is most preferably used from the viewpoint of alkali developability. In addition, when R ⁴ is an organic group, the temperature required for imidization generally tends to be higher than that of polyamic acid, which is preferable because the temperature of post-exposure heating can be lowered and the load on the process can be reduced. .

In the above formula (1), generally, R ¹ is a structure derived from tetracarboxylic acid or tetracarboxylic dianhydride, and R ² is a structure derived from diamine.

As a method for producing the polyimide precursor used in the present invention, a conventionally known method can be applied and is not particularly limited. For example, there is a method of synthesizing a polyamic acid from an acid dianhydride and a diamine. In this method, the acid dianhydride and the diamine react in approximately equimolar amounts, but either the acid dianhydride or the diamine is added in excess from the viewpoint of controlling the molecular weight and viscosity. When acid dianhydride is added excessively, the terminal becomes an acid anhydride (for example, the structure of the above formula (2)). On the other hand, when diamine is added excessively, the terminal becomes an amine (for example, —NH ₂ ).

  Examples of tetracarboxylic dianhydrides applicable to the polyimide precursor in the present invention include, for example, ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic Aliphatic tetracarboxylic dianhydrides such as acid dianhydrides and cyclopentanetetracarboxylic dianhydrides; pyromellitic dianhydrides, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydrides, 2 , 2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,3 ′, 3,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride Anhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,3', 3,4'-biphenyltetracarbonate Boronic acid dianhydride, 2,2 ′, 6,6′-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2 , 3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4 -Dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3 3-hexafluoropropane Water, 1,3-bis [(3,4-dicarboxy) benzoyl] benzene dianhydride, 1,4-bis [(3,4-dicarboxy) benzoyl] benzene dianhydride, 2,2-bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} propane dianhydride, 2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} propane dianhydride Bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, 4 , 4′-bis [4- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, 4,4′-bis [3- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, bis {4 -[4- (1,2-dicarboxy) Phenoxy] phenyl} ketone dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] Phenyl} sulfone dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} sulfone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} Sulfide dianhydride, bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} sulfide dianhydride, 2,2-bis {4- [4- (1,2-dicarboxy) phenoxy] Phenyl} -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} -1,1, 1,3,3,3-F Safluoropropane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis (2,3- or 3 , 4-dicarboxyphenyl) propane dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3 4-benzenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8 -Phenanthrenetetracarboxylic dianhydride, pyridinetetracarboxylic dianhydride, sulfonyldiphthalic anhydride, m-terphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, p-terphenyl −3, 3 ′, , 4′-tetracarboxylic dianhydride, 9,9-bis- (trifluoromethyl) xanthenetetracarboxylic dianhydride, 9-phenyl-9- (trifluoromethyl) xanthenetetracarboxylic dianhydride, 12 , 14-diphenyl-12,14-bis (trifluoromethyl) -12H, 14H-5,7-dioxapentacene-2,3,9,10-tetracarboxylic dianhydride, 1,4-bis (3 , 4-Dicarboxytrifluorophenoxy) tetrafluorobenzene dianhydride, 1,4-bis (trifluoromethyl) -2,3,5,6-benzenetetracarboxylic dianhydride, 1- (trifluoromethyl) -2,3,5,6-benzenetetracarboxylic dianhydride, p-phenylenebistrimellitic acid monoester dianhydride, p-biphenylene vist Aromatic tetracarboxylic dianhydrides such as limellitic acid monoester dianhydride and the like. These may be used alone or in combination of two or more.

On the other hand, a diamine component applicable to the polyimide precursor can be used alone or in combination of two or more diamines. The diamine component used is p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′- Diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3, , 3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,4′-diaminobenzophenone, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 2,2 -Di (3-aminophenyl) Propane, 2,2-di (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2,2-di (3-aminophenyl) -1,1, 1,3,3,3-hexafluoropropane, 2,2-di (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2- (3-aminophenyl) -2 -(4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 1,1-di (3-aminophenyl) -1-phenylethane, 1,1-di (4-amino) Phenyl) -1-phenylethane, 1- (3-aminophenyl) -1- (4-aminophenyl) -1-phenylethane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis ( 4-aminophenoxy) benzene, 1, -Bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminobenzoyl) benzene, 1,3-bis (4-aminobenzoyl) benzene, , 4-bis (3-aminobenzoyl) benzene, 1,4-bis (4-aminobenzoyl) benzene, 1,3-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,3-bis ( 4-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (4-amino-α, α-dimethylbenzyl) benzene 1,3-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,3-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4- Bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 2,6-bis (3-aminophenoxy) benzo Nitrile, 2,6-bis (3-aminophenoxy) pyridine, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (3- Aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-Aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-Aminophenoxy) phenyl] propane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4 -(4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [ 4- (4-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (4-aminophenoxy) benzo L] benzene, 1,3-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] Benzene, 1,4-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 4,4′-bis [4- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-Amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, 4,4′-bis [4- (4-aminophenoxy) phenoxy] diphenylsulfone, 3,3′-dia Mino-4,4′-diphenoxybenzophenone, 3,3′-diamino-4,4′-dibiphenoxybenzophenone, 3,3′-diamino-4-phenoxybenzophenone, 3,3′-diamino-4-biphenoxy Benzophenone, 6,6′-bis (3-aminophenoxy) -3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane, 6,6′-bis (4-aminophenoxy) -3, Aromatic amines such as 3,3 ′, 3′-tetramethyl-1,1′-spirobiindane; 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) ) Tetramethyldisiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω-bis (3-aminobutyl) polydimethylsiloxane, bis (aminomethyl) A Bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, bis (2-aminomethoxy) ethyl] ether, bis [2- (2-aminoethoxy) ethyl] ether, bis [2- ( 3-aminoprotoxy) ethyl] ether, 1,2-bis (aminomethoxy) ethane, 1,2-bis (2-aminoethoxy) ethane, 1,2-bis [2- (aminomethoxy) ethoxy] ethane, 1,2-bis [2- (2-aminoethoxy) ethoxy] ethane, ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether, triethylene glycol bis (3-aminopropyl) ether , Ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diamino Of 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane Such aliphatic amines; 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-di (2-aminoethyl) cyclohexane, 1,3-di (2-aminoethyl) ) Cyclohexane, 1,4-di (2-aminoethyl) cyclohexane, bis (4-aminocyclohexyl) methane, 2,6-bis (aminomethyl) bicyclo [2.2.1] heptane, 2,5- And alicyclic diamines such as bis (aminomethyl) bicyclo [2.2.1] heptane. Examples of guanamines include acetoguanamine, benzoguanamine, and the like, and some or all of the hydrogen atoms on the aromatic ring of the diamine are fluoro group, methyl group, methoxy group, trifluoromethyl group, or trifluoromethoxy group. Diamines substituted with substituents selected from the group can also be used.
Furthermore, depending on the purpose, any one or two or more of the ethynyl group, benzocyclobuten-4′-yl group, vinyl group, allyl group, cyano group, isocyanate group, and isopropenyl group serving as a crosslinking point, Even if it introduce | transduces into some or all of the hydrogen atoms on the aromatic ring of diamine as a substituent, it can be used.

  The polyimide precursors are both aromatic and diamine-derived because they are excellent in heat resistance and insulation in thin films, and have a 5% weight loss temperature increase and outgas reduction. It is desirable to include a group structure. In particular, it is preferable that all of the part derived from the acid dianhydride and the part derived from the diamine are a wholly aromatic polyimide or a wholly aromatic polyimide precursor containing an aromatic structure.

Here, the wholly aromatic polyimide precursor is a polyimide precursor obtained by copolymerization of an aromatic acid component and an aromatic amine component, or polymerization of an aromatic acid / amino component, and a derivative thereof. The aromatic acid component is a compound in which all four acid groups forming the polyimide skeleton are substituted on the aromatic ring, and the aromatic amine component is the two amino groups forming the polyimide skeleton. Both are compounds substituted on the aromatic ring, and the aromatic acid / amino component is a compound in which both the acid group and amino group forming the polyimide skeleton are substituted on the aromatic ring. However, as is clear from the specific examples of the raw material aromatic dianhydride and aromatic diamine, it is not necessary that all acid groups or amino groups exist on the same aromatic ring.
For the above reasons, the polyimide precursor should have a copolymerization ratio of the aromatic acid component and / or aromatic amine component as large as possible when the final polyimide resin is required to have heat resistance and dimensional stability. preferable. Specifically, the proportion of the aromatic acid component in the acid component constituting the repeating unit of the imide structure is preferably 50 mol% or more, particularly preferably 70 mol% or more, and the amine component constituting the repeating unit of the imide structure The proportion of the aromatic amine component in the total is preferably 40 mol% or more, particularly preferably 60 mol% or more, and is preferably a wholly aromatic polyimide or a wholly aromatic polyimide precursor.

In the present invention, it is preferable that 33 mol% or more of R ¹ in the polyimide precursor having the structure represented by the above formula (1) is any structure represented by the following formula (10). In this case, the polyimide resin is excellent in heat resistance and exhibits a low linear thermal expansion coefficient. The content of the structure represented by the following formula is preferably closer to 100 mol% of R ^{1 in} the above formula (1), but among them, the content of the structure represented by the above formula is in the above formula (1). It is preferable that it is 50 mol% or more among R < ¹ > of this, and it is more preferable that it is 70 mol% or more.

(In the formula (10), a is a natural number of 0 or 1 or more, A is a single bond (biphenyl structure), an oxygen atom (ether bond), or an ester bond. The linking group is bonded to the 2, 3 or 3, 4 position of the aromatic ring as viewed from the bonding site of the aromatic ring.)

The acid dianhydride used to make R ¹ in the above formula (1) any one of the structures represented by the above formula (10) includes 3,3 ′, 4,4′-biphenyltetracarboxylic acid. Dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,3,2 ′, 3′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) Examples include ether dianhydride, p-phenylenebistrimellitic acid monoester dianhydride, p-biphenylenebistrimellitic acid monoester dianhydride, and the like. These are preferable from the viewpoint of reducing the hygroscopic expansion coefficient and from the viewpoint of expanding the selectivity of the diamine.

  As the tetracarboxylic dianhydride used in combination, a tetracarboxylic dianhydride having a fluorine atom can be used. When tetracarboxylic dianhydride into which fluorine is introduced is used, the hygroscopic expansion coefficient of the finally obtained polyimide resin is lowered. The tetracarboxylic dianhydride having at least one fluorine atom preferably has a fluoro group, a trifluoromethyl group, or a trifluoromethoxy group. Specific examples include 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride. However, when the polyimide precursor has a skeleton containing fluorine, the polyimide precursor tends to be difficult to dissolve in a basic aqueous solution. Therefore, when performing patterning, an organic solvent such as alcohol and a basic aqueous solution are used. It may be necessary to develop with a mixed solution. The same applies to the case where a skeleton containing fluorine is included as a diamine component described later.

Moreover, in the said polyimide precursor, it is preferable that 33 mol% or more among R < ² > in said Formula (1) is one of the structures represented by following formula (11). In this case, the polyimide resin is excellent in heat resistance and exhibits low linear thermal expansion and low hygroscopic expansion. The content of the structure represented by the following formula (11) is preferably as close as possible to 100 mol% of R ^{2 in} the above formula (1), but among them, the content of the structure represented by the above formula is preferably the above formula ( preferably 1) is 50 mol% or more of R ² a, is preferably more than 70 mol%.

(In the formula (11), R ²⁷ is a divalent organic group, oxygen atom, sulfur atom, or sulfone group. In addition, a part or all of the hydrogen atoms on the aromatic ring may be halogen atoms, alkyl groups, or methoxy groups. , May be substituted with a substituent selected from a trifluoromethyl group or a trifluoromethoxy group.)

Specific examples of the diamine used to make R ² in the above formula (1) any one of the structures represented by the above formula (11) include p-phenylenediamine, m-phenylenediamine, 1, 4-diaminonaphthalene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 1,4-diaminoanthracene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2, 2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 3,3′-dichloro-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3, 3'-dimethyl-4,4'-diaminobiphenyl and the like can be mentioned.
Introducing fluorine as a substituent of the aromatic ring as in 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl is preferable because the hygroscopic expansion coefficient of the polyimide resin can be reduced.

  The polyimide precursor used in the present invention has an exposure wavelength when the film thickness is 1 μm in order to increase the sensitivity when the photosensitive polyimide resin composition is used and to obtain a pattern shape that accurately reproduces the mask pattern. On the other hand, it is preferable that the transmittance is at least 5% or more, and it is more preferable that the transmittance is 15% or more.

In addition, when exposure is performed using a high-pressure mercury lamp, which is a general exposure light source, a transmittance with respect to an electromagnetic wave having a wavelength of at least 436 nm, 405 nm, and 365 nm is formed on a film having a thickness of 1 μm. Is preferably 5% or more, more preferably 15%, and still more preferably 50% or more.
The high transmittance of the polyimide precursor with respect to the exposure wavelength means that the loss of light is small, and a highly sensitive photosensitive polyimide resin composition can be obtained.

  In order to increase the transmittance as the polyimide precursor, it is possible to reduce hygroscopic expansion while maintaining heat resistance by using an acid dianhydride or diamine introduced with fluorine as described above. It is preferable from a certain point. In order to increase the transmittance, acid dianhydride or diamine having an alicyclic skeleton may be used, but heat resistance may be lowered.

  On the other hand, when a diamine or acid dianhydride having a siloxane skeleton such as 1,3-bis (3-aminopropyl) tetramethyldisiloxane is used as the diamine or acid dianhydride, the adhesion to the substrate can be improved. The elastic modulus of the polyimide resin can be lowered, and the glass transition temperature can be lowered.

Next, the terminal of the polyimide precursor used for this invention is demonstrated.
At least a part of the terminals of the polyimide precursor used in the present invention is an organic group represented by the following formulas (2) to (5). In particular, in the case of a terminal organic group represented by the following formula (5), an amino group is generated during post-exposure heating, and the development rate of the unexposed portion is decreased. Are preferably those that do not decompose into amino groups. Whether the sealing group is decomposed by heating can be confirmed by the following method. For example, after heating a resin having a sealing group introduced at 150 ° C., the resin is directly measured by pyrolysis gas chromatograph (PGC), infrared spectrum, ¹ H-NMR spectrum, or ¹³ C-NMR spectrum. Whether or not the sealing group is decomposed can be confirmed. In addition, by dissolving the resin into which the sealing group is introduced in an acidic solution, it is decomposed into an amine component and an acid anhydride component which are the structural units of the resin, and this is analyzed by gas chromatography (GC) or NMR measurement. Also, it can be confirmed whether or not the sealing group is decomposed.

(In Formula (2), R ⁵ is a tetravalent organic group, and R ⁶ is a hydrogen atom or a monovalent organic group.)

(In Formula (3), R ⁷ is a tetravalent organic group, R ⁸ is a hydrogen atom or a monovalent organic group. Plural R ^8s may be the same or different.)

(In Formula (4), R ⁹ is a tetravalent organic group, R ¹⁰ and R ¹¹ are a hydrogen atom or a monovalent organic group. Plural R ^10s may be the same or different.)

(In formula (5), X is a C, P or S atom, Y is an S or O atom, Z is —R ¹² or —OR ¹³ , and R ¹² and R ¹³ are monovalent organic groups.)

R ⁵ , R ⁷ and R ⁹ are tetravalent organic groups, and usually have a structure derived from the same tetracarboxylic acid or tetracarboxylic dianhydride as R ¹ . The tetracarboxylic dianhydride may be the same as those listed as the tetracarboxylic dianhydride applicable to the polyimide precursor. Examples of the tetracarboxylic acid include those obtained by hydrolyzing the acid anhydride group of the tetracarboxylic dianhydride cited as the tetracarboxylic dianhydride applicable to the polyimide precursor to form a carboxyl group.

R ⁶ , R ⁸ and R ¹⁰ are a hydrogen atom or a monovalent organic group, and the monovalent organic group may be the same as those exemplified as R ³ , for example.
R ⁶ , R ⁸ and R ¹⁰ are preferably hydrogen atoms from the viewpoint of increasing solubility in a basic aqueous solution.

R ¹¹ is a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and C _n H _2n OC containing an ether bond therein. A structure represented by _m H _{2m + 1 and the} like can be given.

In the above formula (5), X is a C, P or S atom, Y is an S or O atom, and combinations of X and Y atoms are -C (= O)-, -C (= S)- , -P (= O)-, -S (= O)-, and the like. Among these, a combination in which X is a carbon atom and Y is an oxygen atom is preferable from the viewpoint of easy availability of the end-capping agent and easy handling.

R ¹² and R ¹³ are monovalent organic groups, and are represented by, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and C _n H _2n OC _m H _{2m + 1} containing an ether bond therein. The structure etc. can be mentioned.

  The above formula (5) is, among other things, an organic group represented by the following formula (6). When the polyimide precursor is imidized, the sealing group is also imidized at the same time. In the case of high heat resistance and low hygroscopicity.

(In the formula (6), R ¹⁴ is an organic group selected from the group consisting of organic groups represented by the following formulas (6-1) to (6-5), and R ¹⁵ is a hydrogen atom or a monovalent organic group. is there.)

(In the formulas (6-1) to (6-5), A each independently represents a hydrogen atom or an organic group, which may be the same or different. (It may be bonded to form a cyclic structure and may contain a heteroatom bond. -COOR corresponds to -COOR ¹⁵ in formula (6).)

  The compound forming the terminal of the above formula (6) is preferably a divalent having two adjacent carbon skeletons such as phthalic anhydride, maleic anhydride, nadic anhydride, and cyclohexanedicarboxylic anhydride. The thing derived from an organic group is mentioned.

It is not particularly restricted but includes further may have a substituent R ¹⁴ and R ^15, such as a hydrocarbon group of 1 to 5 carbon atoms, a halogen atom, a hydroxyl group, a carbonyl group, a nitro group and the like, double bonds You may have a triple bond.

  The formation method of the terminal of the polyimide precursor used for this invention is not specifically limited, A well-known method can be used. For example, in the method of synthesizing from the acid dianhydride and the diamine, when the acid dianhydride is excessively added to the diamine, that is, the acid dianhydride is 100 to 125 mol, preferably 100.01 mol per 100 mol of the diamine. When added to ˜120 mol, more preferably 100.1 to 115 mol, an acid anhydride-terminated polyimide precursor exhibiting properties suitable for the present invention is obtained. The end of the polyimide precursor is preferably 70% or more if it is a group represented by the above formula (2) or (3), but more preferably 90% or more. Furthermore, the terminal becomes a group represented by the above formula (4) by sealing the terminal with monoamine by a known method. From the viewpoint of improving heat resistance and reducing hygroscopicity when polyimide is used, the terminal is preferably a group represented by the above formula (4).

Monoamines used as end capping agents include 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy. -4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4 -Aminobenzoic acid, 4-aminosalicylic acid, 5-amino Salicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4 -Aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like are preferable. Two or more of these may be mixed and used.

On the other hand, in the method of synthesizing from the acid dianhydride and the diamine, when diamine is added excessively with respect to the acid dianhydride, that is, 100 to 125 mol, preferably 100. When added in an amount of 01 to 120 mol, more preferably 100.1 to 115 mol, an amine-terminated polyimide precursor exhibiting properties suitable for the present invention is obtained. The end of the polyimide precursor is preferably 70% or more amino groups, but more preferably 90% or more.
By sealing the amine terminal with a terminal blocking agent, the terminal becomes a group represented by the above formula (5).

  Examples of the terminal blocking agent include acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds. In particular, when an acid anhydride is used, the terminal is preferable in that it becomes a group represented by the above formula (6).

  Although the specific example of the acid anhydride used suitably as a terminal blocker is shown below, it is not limited to these.

It is sufficient that at least a part of the amine terminal is sealed, that is, if at least a part of R ⁴ in the formula (1) is an organic group, pseudo-crosslinking is reduced and the solubility in a developer is reduced. improves. Among them, 50% or more of R ⁴ is preferably an organic group from the viewpoint of further shortening the development time, and more preferably 70% or more. Further, it is more preferable that 50% or more of the R ⁴ is an organic group represented by the formula (6) from the viewpoint that the dissolution rate ratio between the exposed area and the unexposed area can be further increased, and it is 70% or more. Is more preferable. In the case where 50% or more of R ⁴ is an organic group, it is considered that the ratio of those in which both ends of the polyimide precursor are both amino groups is remarkably reduced. As a result, as shown in FIG. 2, the number of polyimide precursor molecules that interact with the carboxyl group decreases so as to crosslink two polyimide precursors, so that the solubility in a developer is improved and the development speed is high. Presumed to be.

  The method of terminal sealing is not specifically limited, A well-known method can be used. For example, the method described in Japanese Patent Application Laid-Open No. 60-212504 can be mentioned. In this method, first, a part of the diamine is replaced with a monoamine which is a terminal blocking agent, or a part of the acid dianhydride is replaced with an acid anhydride which is a terminal blocking agent, and the terminal is blocked. Polyimide precursors can be made. In the former case, the end is as shown in formula (4), and in the latter case, the end is as shown in formula (5).

  Moreover, after adding acid dianhydride excessively with respect to diamine and making it react, terminal blocker (monoamine) is added directly in a reaction liquid, or the copolymer of acid dianhydride and diamine is once reaction liquid. Then, after being purified or dried, the acid anhydride terminal can be sealed by dissolving in an organic solvent again and adding a terminal blocking agent (monoamine). In this case, the end is as shown in Formula (4).

  In addition, the diamine is added in excess to the acid dianhydride to cause the reaction, and a terminal blocking agent (an acid anhydride or the like) is directly added to the reaction solution, or the copolymer of the acid dianhydride and the diamine is temporarily added. After purification from the reaction solution and drying, the amine terminal can be blocked by dissolving in an organic solvent again and adding a terminal blocking agent (such as an acid anhydride). In this case, the end is as shown in Formula (5).

  The introduction ratio of the monoamine used for the terminal blocking agent is preferably in the range of 0.01 to 25 mol%, particularly preferably 0.1 to 20 mol%, and more preferably 0.1 to 15 mol based on the total amine component. More preferred is mol%. The introduction ratio of the compound selected from the acid anhydride, monocarboxylic acid, monoacid chloride compound and monoactive ester compound used as the end-capping agent ranges from 0.1 to 100 mol% with respect to the diamine component. Preferably, it is 50 mol%-100 mol%, More preferably, it is 70 mol%-100 mol%. A plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

The end-capping agent introduced into the resin can be easily detected by the following method. For example, the resin into which the end-capping agent has been introduced can be detected by directly measuring a pyrolysis gas chromatograph (PGC), infrared spectrum, ¹ H-NMR spectrum, or ¹³ C-NMR spectrum. In addition, the resin in which the end-capping agent is introduced is dissolved in an acidic solution and decomposed into an amine component and an acid anhydride component, which are constituent units of the resin, and this is measured by gas chromatography (GC) or NMR. The end-capping agent can also be detected.

The weight average molecular weight of the polyimide precursor used in the present invention is preferably in the range of 3,000 to 1,000,000, and preferably in the range of 5,000 to 500,000, although it depends on the application. Is more preferable, and the range of 6,000 to 250,000 is more preferable. When the weight average molecular weight is less than 3,000, it is difficult to obtain sufficient strength when a coating film or film is used. In addition, the strength of the film is reduced when a heat treatment or the like is performed to obtain a polymer such as a polyimide resin. On the other hand, when the weight average molecular weight exceeds 1,000,000, the viscosity increases and the solubility decreases, so that it is difficult to obtain a coating film or film having a smooth surface and a uniform film thickness.
The weight average molecular weight used here refers to a value in terms of polystyrene measured by gel permeation chromatography (GPC), may be a molecular weight obtained by measuring the polyimide precursor itself, or may be chemically imidized with acetic anhydride or the like. What was measured after performing may be sufficient.
Further, when it is difficult to measure the weight average molecular weight, the number average molecular weight can be substituted. The number average molecular weight in this case can be calculated by a technique such as directly measuring the ¹ H-NMR spectrum, ¹³ C-NMR spectrum, etc. of the resin into which the end-capping agent is introduced, and quantifying the end of the molecular chain. is there. Moreover, it can also obtain as an approximate value from the addition amount of the acid dianhydride-derived component and the diamine-derived component, the addition amount of the end-capping component, etc. when synthesizing the polyimide precursor.
In the present invention, if either the weight average molecular weight or the number average molecular weight is within the above range, good characteristics can be obtained as the photosensitive polyimide resin composition.

As the content of the polyimide precursor used in the present invention, film physical properties of the resulting pattern,
In particular, from the viewpoint of film strength and heat resistance, it is preferably 50% by weight or more, more preferably 70% by weight or more, based on the entire solid content of the negative photosensitive polyimide resin composition.
In addition, solid content is all components other than a solvent, and a liquid monomer component is also contained in solid content.

1-2. Photobase generator The photobase generator in the present invention generates a base by exposure, and the base serves as a catalyst for curing the polyimide precursor by heating.
The photosensitive component contained in the negative photosensitive polyimide resin composition is contained in order to cure only the exposed portion after exposure of the polyimide precursor. In the present invention, a photobase generator is used.

As content of the photosensitive component used for this invention, if a desired pattern can be formed, it will not specifically limit, It can be set as general content.
In the present invention, the photosensitive component is preferably in the range of 0.1 part by weight or more and less than 30 parts by weight with respect to 100 parts by weight of the polyimide precursor. It is preferably within the range of 25 parts by weight, and particularly preferably within the range of 0.5 to 20 parts by weight.

  In the system according to the present invention, a photobase generator is added to a polyimide precursor and the imidization reaction is catalytically accelerated by a base generated by light irradiation, and the exposed portion is selectively insolubilized. Patterning is possible by addition, and it is not necessary to introduce a crosslinking component or a degradable substituent, so that the amount of additive can be further reduced. The content of the photosensitive component contained in a general photosensitive polyimide resin composition is more than 30 parts by weight with respect to 100 parts by weight of the polyimide precursor, whereas the photobase generator is the above-mentioned. Thus, the generated chemical species act catalytically, so that the exposure sensitivity can be sufficiently cured even when the content is within the above-described range. In addition, the photobase generator has lower heat resistance than the polyimide precursor and can be the main component of outgas after becoming a cured film. Therefore, by reducing the content as described above, The amount of outgas generation after the cured film can be made sufficiently small.

In the present invention, the photosensitive component is mainly composed of a photobase generator. This is because a base which is a generated chemical species is preferable to using an acid generator as compared with an acid which has almost no imidation catalytic action and easily corrodes a metal.
In addition, the main component means that the content of the photobase generator in the photosensitive component is 50% by mass or more.
The photobase generator used in the present invention is not active under normal conditions of normal temperature and pressure, but generates a base (basic substance) when subjected to electromagnetic wave irradiation and heating as an external stimulus. If it is, it will not specifically limit.

In the present invention, known photobase generators can be used. For example, M.M. Shirai, and M.M. Tsunooka, Prog. Polym. Sci. , 21, 1 (1996); Masahiro Kadooka, polymer processing, 46, 2 (1997); Kutal, Coord. Chem. Rev. , 211, 353 (2001); Kaneko, A .; Sarker, and D.C. Neckers, Chem. Mater. 11, 170 (1999); Tachi, M .; Shirai, and M.M. Tsunooka, J. et al. Photopolym. Sci. Technol. , 13, 153 (2000); Winkle, and K.K. Graziano, J. et al. Photopolym. Sci. Technol. 3,419 (1990); Tsunooka, H .; Tachi, and S.M. Yoshitaka, J. et al. Photopolym. Sci. Technol. , 9, 13 (1996); Suyama, H .; Araki, M .; Shirai, J. et al. Photopolym. Sci. Technol. , 19, 81 (2006), as described in transition metal compound complexes, those having a structure such as an ammonium salt, and those formed by salt formation of an amidine moiety with a carboxylic acid, An ionic compound neutralized by forming a salt with a base component, or a nonionic compound in which the base component is made latent by a urethane bond or an oxime bond such as a carbamate derivative, an oxime ester derivative, or an acyl compound. Can be mentioned.
The photobase generator used in the present invention is not particularly limited and known ones can be used. For example, carbamate derivatives, amide derivatives, imide derivatives, α-cobalt complexes, imidazole derivatives, cinnamic acid amide derivatives, oxime derivatives. Etc.

Although it does not specifically limit as a basic substance generate | occur | produced from the photobase generator used for this invention, The compound which has an amino group, especially polyamines, such as a monoamine and diamine, Amidine, etc. are mentioned.
The generated basic substance is preferably a compound having an amino group having a higher basicity. This is because the catalytic action for the dehydration condensation reaction or the like in the imidization of the polyimide precursor is strong, and the catalytic effect in the dehydration condensation reaction or the like at a lower temperature can be expressed with a smaller amount of addition. That is, since the catalytic effect of the generated basic substance is great, the apparent sensitivity as the photosensitive resin composition is improved.
From the viewpoint of the catalytic effect, an amidine and an aliphatic amine are preferable.

  The photobase generator according to the present invention is preferably a photobase generator that does not contain a salt in the structure, and preferably has no charge on the nitrogen atom of the base moiety generated in the photobase generator. As the photobase generator according to the present invention, it is preferable that the generated base is latentized using a covalent bond, and the base generation mechanism is between a nitrogen atom of the generated base portion and an adjacent atom. It is preferable that the covalent bond is cleaved to generate a base. When the base generator does not contain a salt in the structure, the base generator can be neutralized, so that the solvent solubility is good and the pot life is improved. For these reasons, the amine generated from the photobase generator used in the present invention is preferably a primary amine or a secondary amine.

For the above reasons, as the photobase generator, it is preferable that the generated base is latentized using a covalent bond as described above, and the generated base has an amide bond, carbamate bond, or oxime bond. It is preferably latentized by using.
Examples of the base generator according to the present invention include a base generator having a cinnamic amide structure as disclosed in JP2009-80452A and WO2009 / 123122, and JP2006-189591A. Base generators having a carbamate structure as disclosed in Japanese Patent Application Laid-Open No. 2008-247747, and oxime structures and carbamoyloxime structures as disclosed in Japanese Patent Application Laid-Open Nos. 2007-249013 and 2008-003581 However, it is not limited thereto, and other known base generator structures can be used.

Hereinafter, the photobase generator used in the present invention will be described with specific examples.
Examples of the ionic compound include those having the following structural formula.

  Examples of the acyl compound include compounds represented by the following formula.

  Moreover, as a photobase generator used by this invention, the compound shown to following General formula (7) is mentioned, for example.

(In Formula (7), R ⁴¹ and R ⁴² each independently represent a hydrogen atom or an organic group, and may be the same or different. R ⁴¹ and R ⁴² are bonded to form a ring. It may form a structure and may contain a bond of hetero atoms, provided that at least one of R ⁴¹ and R ⁴² is an organic group, and R ⁴³ and R ⁴⁴ are each independently a hydrogen atom, A halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, or organic group, may be different even in the same ^{.R 45, R 46,} R ⁴⁷ and ^{R 48} are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, Sulf Group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group or organic group, which are the same. Two or more of R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ may be bonded to form a cyclic structure, and may contain a hetero atom bond. R ⁴⁹ is a hydrogen atom or a protecting group that can be deprotected by heating and / or irradiation with electromagnetic waves.)

When the base generator represented by the chemical formula (7) is irradiated with electromagnetic waves, as shown by the following formula, (-CR ⁴⁴ = CR ⁴³ -C (= O) in the formula (7) The-) moiety isomerizes from the trans form to the cis form. Furthermore, when R ⁴⁹ is a protecting group by heating and / or irradiation with electromagnetic waves, the protecting group R ⁴⁹ is deprotected and cyclized to produce a base (NHR ⁴¹ R ⁴² ). In the base generator represented by the chemical formula (7), the hydroxyl group at the ortho position of the carbon-carbon double bond is used for intramolecular cyclization for base generation. Therefore, in addition to the structure in which the hydroxyl group at the ortho position is protected by a protecting group, the group having the blocked covalent bond-forming group of the present invention is provided.

In the chemical formula (7), R ⁴¹ and R ⁴² are each independently a hydrogen atom or an organic group, but at least one of R ¹ and R ² is an organic group. ^{Further, NHR} 41 ^{R 42} is a ^{base, R 41} and ^{R 42,} respectively, is preferably an organic group containing no amino group. If an amino group is contained in R ⁴¹ and R ⁴² , the base generator itself becomes a basic substance, which accelerates the reaction of the polymer precursor, and the solubility contrast between the exposed and unexposed areas is increased. There is a risk of the difference becoming smaller. However, when there is a difference in basicity between the irradiation with electromagnetic waves and the base generated after heating, such as when an amino group is bonded to the aromatic ring present in the organic group of R ⁴¹ and R ^42. May be used even if the organic group of R ⁴¹ and R ⁴² contains an amino group.
Examples of the organic group include a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, an aryl group, an aralkyl group, and a saturated or unsaturated halogenated alkyl group. These organic groups may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group, and these may be linear, branched or cyclic.
The organic group is preferably a linear, branched or cyclic hydrocarbon group which may contain a substituent, may contain an unsaturated bond, and may contain a heteroatom bond.
The organic group in R ⁴¹ and R ⁴² is usually a monovalent organic group. However, in the case of forming a cyclic structure to be described later, the generated NHR ⁴¹ R ⁴² is an NH group capable of forming an amide bond such as diamine. In the case of a basic substance having two or more, it can be a divalent or higher organic group.

R ⁴¹ and R ⁴² may be bonded to form a cyclic structure.
The cyclic structure is a combination of two or more selected from the group consisting of saturated or unsaturated alicyclic hydrocarbons, heterocycles, and condensed rings, and the alicyclic hydrocarbons, heterocycles, and condensed rings. The structure which becomes may be sufficient.

The bond other than the hydrocarbon group in the organic group of R ⁴¹ and R ⁴² is not particularly limited as long as the effect of the present invention is not impaired, and is an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond. Amide bond, urethane bond, imino bond (-N = C (-R)-, -C (= NR)-, where R is a hydrogen atom or an organic group), carbonate bond, sulfonyl bond, sulfinyl bond, azo bond Etc. From the viewpoint of heat resistance, the bond other than the hydrocarbon group in the organic group includes an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, and an imino bond (—N═C (— R)-, -C (= NR)-: where R is a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, and a sulfinyl bond.

Substituents other than the hydrocarbon group in the organic group of R ⁴¹ and R ⁴² , that is, a substituent included in the organic group, which is different from the hydrocarbon group, and may be substituted with a hydrocarbon group. The substituent is not particularly limited as long as the effect of the present invention is not impaired, and is not limited to a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group, a cyanato group, an isocyanato group, a thiocyanato group, an isothiocyanato group, a silyl group. Group, silanol group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, Phosphono group, phosphonato group, hydroxyimino group, saturated or unsaturated alkyl A ruether group, a saturated or unsaturated alkylthioether group, an arylether group, an arylthioether group, an amino group (—NH2, —NHR, —NRR ′: where R and R ′ are each independently a hydrocarbon group), etc. Can be mentioned. The hydrogen atom contained in the substituent may be substituted with a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be any of linear, branched, and cyclic.
Examples of the substituent other than the hydrocarbon group in the organic group of R ⁴¹ and R ⁴² include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group, a cyanato group, an isocyanato group, a thiocyanato group, an isothiocyanato group, Silyl group, silanol group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group A phosphono group, a phosphonato group, a hydroxyimino group, a saturated or unsaturated alkyl ether group, a saturated or unsaturated alkyl thioether group, an aryl ether group, and an aryl thioether group.

Since the basic substance to be generated is NHR ⁴¹ R ⁴² , examples thereof include primary amines, secondary amines, and heterocyclic compounds. The amine includes an aliphatic amine and an aromatic amine, respectively. In addition, the heterocyclic compound here means that NHR ⁴¹ R ⁴² has a cyclic structure and has aromaticity. Non-aromatic heterocyclic compounds that are not aromatic heterocyclic compounds are included here in aliphatic amines as alicyclic amines.

Furthermore, the NHR ⁴¹ R ^{42 to be} produced is not only a basic substance such as a monoamine having only one NH group capable of forming an amide bond, but also 2 NH groups capable of forming an amide bond such as diamine, triamine and tetraamine. It may be a basic substance having two or more. In the case where the generated NHR ⁴¹ R ⁴² is a basic substance having two or more NH groups, an amide bond is formed at one or more terminals of R ⁴¹ and / or R ^{42 in} the formula (8) or formula (9). Examples include a structure in which a photolatent moiety that generates a base having a possible NH group by irradiation with electromagnetic waves and heating is further bonded. As the photolatent site, to one or more ends of the ^{R 41} and / or ^{R 42} of said formula (8) or (9), the formula (8) or ^{R 41} and / or the formula (9) residue obtained by removing the R ⁴² can be mentioned a structure is further bonded.

  Aliphatic primary amines include methylamine, ethylamine, propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, pentylamine, isoamylamine, tert-pentylamine, cyclopentylamine, hexylamine, cyclohexylamine , Heptylamine, cycloheptaneamine, octylamine, 2-octaneamine, 2,4,4-trimethylpentan-2-amine, cyclooctylamine and the like.

  Examples of the aromatic primary amine include aniline, 2-aminophenol, 3-aminophenol, and 4-aminophenol.

  Aliphatic secondary amines include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, ethylmethylamine, aziridine, azetidine, pyrrolidine, piperidine, azepan, azocan, methylaziridine, dimethylaziridine, methylazetidine, dimethyl Examples thereof include azetidine, trimethylazetidine, methylpyrrolidine, dimethylpyrrolidine, trimethylpyrrolidine, tetramethylpyrrolidine, methylpiperidine, dimethylpiperidine, trimethylpiperidine, tetramethylpiperidine, pentamethylpiperidine and the like, among which alicyclic amine is preferable.

  Aromatic secondary amines include methylaniline, diphenylamine, and N-phenyl-1-naphthylamine. In addition, as an aromatic heterocyclic compound having an NH group capable of forming an amide bond, an imino bond (—N═C (—R) —, —C (═NR) —, Here, R preferably has a hydrogen atom or an organic group), and examples thereof include imidazole, purine, triazole, and derivatives thereof.

As amines higher than diamine, ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, Linear aliphatic alkylenediamines such as 1,9-nonanediamine and 1,10-decanediamine; 1-butyl-1,2-ethanediamine, 1,1-dimethyl-1,4-butanediamine, 1-ethyl- 1,4-butanediamine, 1,2-dimethyl-1,4-butanediamine, 1,3-dimethyl-1,4-butanediamine, 1,4-dimethyl-1,4-butanediamine, 2,3- Branched aliphatic alkylenediamines such as dimethyl-1,4-butanediamine; diethylenetriamine, triethylenetetramine, tetraethylenepenta Formula _{NH 2 (CH 2 CH 2 NH} ) polyethylene amines represented by n _H such emissions; cyclohexane diamine, methylcyclohexane diamine, isophorone diamine, norbornane dimethylamine, tricyclodecane dimethylamine, alicyclic such as menthenediamine Formula diamines; aromatic diamines such as p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 4,4′-diaminodiphenylmethane, diaminodiphenylsulfone; benzenetriamine, melamine, 2,4 And triamines such as 2,6-triaminopyrimidine; and tetraamines such as 2,4,5,6-tetraaminopyrimidine.

Depending on the substituents introduced at the positions of R ⁴¹ and R ⁴² , the thermophysical properties and basicity of the basic substance to be generated are different.
Catalytic action, such as lowering the reaction start temperature for the reaction from the polymer precursor to the final product, is more effective as a catalyst with a basic substance having a higher basicity, and a lower temperature with a smaller amount of addition. Reaction to the final product is possible. In general, secondary amines have higher basicity than primary amines, and their catalytic effect is greater.
In addition, aliphatic amines are preferred over aromatic amines because they are more basic.

  Further, when the base generated in the present invention is a secondary amine and / or a heterocyclic compound, it is preferable from the viewpoint of increasing the sensitivity as a base generator. It is presumed that this is because the use of a secondary amine or a heterocyclic compound eliminates active hydrogen at the amide bond site, thereby changing the electron density and improving the sensitivity of isomerization.

Further, from the viewpoint of the thermophysical properties of the base to be eliminated and the basicity, the organic groups of R ⁴¹ and R ⁴² each independently preferably have 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably carbon. It is preferable that it is number 1-8.

In the chemical formula (7), R ⁴³ and R ⁴⁴ are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group. , Sulfonate groups, phosphino groups, phosphinyl groups, phosphono groups, phosphonate groups, or organic groups, which may be the same or different. R ⁴³ and R ⁴⁴ may have a blocked covalent bond forming group.
R ⁴³ and R ⁴⁴ are each preferably a hydrogen atom from the viewpoint of easily achieving high sensitivity.

In the present invention, in particular, when at least one of R ⁴³ and R ^{44 in} the chemical formula (8) is not a hydrogen atom but the specific functional group, both of R ⁴³ and R ⁴⁴ are hydrogen atoms. Compared to the case, the base generator of the present invention can further improve the solubility in an organic solvent or improve the affinity with a polymer precursor. For example, when at least one of R ⁴³ and R ⁴⁴ is an organic group such as an alkyl group or an aryl group, the solubility in an organic solvent is improved. For example, when at least one of R ⁴³ and R ⁴⁴ is a halogen atom such as fluorine, the affinity with a polymer precursor containing a halogen atom such as fluorine is improved. For example, when at least one of R ⁴³ and R ⁴⁴ has a silyl group or a silanol group, the affinity with the polysiloxane precursor is improved. Thus, R ⁴³ and / or R ⁴⁴ is combined with a desired organic solvent or polymer precursor, and a substituent is appropriately introduced, so that the solubility in the desired organic solvent and the desired polymer precursor can be reduced. It is possible to improve the affinity.

The halogen atom, organic group, as long as the effects of the present invention are not impaired, it is not particularly limited, and may be the same as those listed R ⁴⁵ to R ^48, which will be described later.
The organic group in R ⁴³ and R ⁴⁴ is usually a monovalent organic group.

When R ⁴³ and R ⁴⁴ have a substituent, at least one of them is an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, or a propyl group; and having 4 to 23 carbon atoms such as a cyclopentyl group or a cyclohexyl group. A cycloalkyl group; a cycloalkenyl group having 4 to 23 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group; an aryloxyalkyl group having 7 to 26 carbon atoms such as a phenoxymethyl group, a 2-phenoxyethyl group and a 4-phenoxybutyl group (-ROAr group); Aralkyl group having 7 to 20 carbon atoms such as benzyl group and 3-phenylpropyl group; Alkyl group having 2 to 21 carbon atoms having cyano group such as cyanomethyl group and β-cyanoethyl group; Hydroxymethyl group An alkyl group having 1 to 20 carbon atoms having a hydroxyl group such as, an alkoxy group having 1 to 20 carbon atoms such as a methoxy group and an ethoxy group, Acetamide group, benzenesulfonyl cyanamide group _{(C 6 H 5 SO 2 NH} 2 -) amide group having a carbon number of 2 to 21, such as a methylthio group, an alkylthio group having 1 to 20 carbon atoms such as an ethylthio group (-SR group) , An acyl group having 1 to 20 carbon atoms such as acetyl group and benzoyl group, an ester group having 2 to 21 carbon atoms such as methoxycarbonyl group and acetoxy group (-COOR group and -OCOR group), phenyl group, naphthyl group, biphenyl An aryl group having 6 to 20 carbon atoms such as a group or tolyl group, an aryl group having 6 to 20 carbon atoms substituted by an electron donating group and / or an electron withdrawing group, an electron donating group and / or an electron withdrawing group. A substituted benzyl group, a cyano group, and a methylthio group (—SCH ₃ ) are preferred. The alkyl moiety may be linear, branched or cyclic.

R ^{45 to} R ^{48 in} the chemical formula (7) are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group. , Sulfonate groups, phosphino groups, phosphinyl groups, phosphono groups, phosphonate groups, amino groups, ammonio groups or organic groups, which may be the same or different. Two or more of R ^{45 to} R ⁴⁸ may be bonded to each other to form a cyclic structure, or may include a hetero atom bond.

It is preferable to introduce one or more substituents into R ^{45 to} R ⁴⁸ in the chemical formula (7). In particular, in the case of the base generator represented by the chemical formula (7), the double bond between the α-carbon and β-carbon located at the α-position and β-position of the carbonyl bond makes the isomerization reaction from the trans isomer to the cis isomer more efficient. There are several factors that may proceed, for example, the carbon - size carbon double bonds around the steric hindrance, the carbon - the electron state of the conjugated chain extending carbon double bond surrounding the like, the substituent R ⁴⁵ a to R ^48, by at least one introducing such substituents as described above, the carbon - can conjugated chain of carbon-carbon double bonds around expands and improves the sensitivity of the base generator. In addition, in R ^{45 to} R ⁴⁸ , the wavelength of light to be absorbed can be adjusted by introducing at least one substituent as described above, and a desired wavelength can be absorbed by introducing a substituent. It can also be made to do. The absorption wavelength can be shifted to a longer wavelength by introducing a substituent that extends the conjugated chain of the aromatic ring. It is also possible to improve the solubility and compatibility with the polymer precursor to be combined. Thereby, it is possible to improve the sensitivity of the photosensitive resin composition in consideration of the absorption wavelength of the polymer precursor to be combined.

  As a guideline of what substituents should be introduced to shift the absorption wavelength with respect to a desired wavelength, the Interspection of the Ultraviolet Products (AI Scott 1964) and the spectrum of organic compounds The table described in the identification method 5th edition (RM Silverstein 1993) can be referred to. By referring to these, it is possible to know a measure of how long the maximum absorption wavelength of the compound is increased.

In R ^{45 to} R ⁴⁸ , examples of the halogen atom include fluorine, chlorine, bromine and the like.
In R ^{45 to} R ⁴⁸ , examples of the organic group include a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, an aryl group, an aralkyl group, and a saturated or unsaturated halogenated alkyl group. These organic groups may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group, and these may be linear, branched or cyclic. As the bond other than the hydrocarbon group in the organic group of R ^{45 to} R ⁴⁸ , the same bond as the bond other than the hydrocarbon group of R ⁴¹ and R ⁴² can be used. The organic group of R ⁴⁵ to R ⁴⁸ may be bonded to the benzene ring via a bond other than a hydrocarbon group. In addition, in the organic group of R ^{45 to} R ⁴⁸ , a substituent other than a hydrocarbon group (a substituent included in the organic group, a substituent different from the hydrocarbon group, and a substituent that may be substituted with a hydrocarbon group) ) May be the same as the substituents other than the hydrocarbon groups of R ⁴¹ and R ⁴² .
The organic group is not particularly limited as long as the effect of the present invention is not impaired, and is a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, an aryl group, an aralkyl group, and a saturated or unsaturated halogenated alkyl group. , Cyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, carboxyl group, carboxylate group, acyl group, acyloxy group, hydroxyimino group, saturated or unsaturated Examples thereof include a saturated alkyl ether group, a saturated or unsaturated alkyl thioether group, an aryl ether group, and an aryl thioether group.
The organic group in R ^{45 to} R ⁴⁸ is usually a monovalent organic group, but may form a divalent or higher organic group in the case of forming a cyclic structure to be described later.

Moreover, two or more of R ^{45 to} R ⁴⁸ may be bonded to form a cyclic structure.
The cyclic structure is a combination of two or more selected from the group consisting of saturated or unsaturated alicyclic hydrocarbons, heterocycles, and condensed rings, and the alicyclic hydrocarbons, heterocycles, and condensed rings. The structure which becomes may be sufficient. For example, each of R ^{45 to} R ⁴⁸ may be a combination of two or more of them, and share a benzene ring atom to which each of R ^{45 to} R ⁴⁸ is bonded, such as naphthalene, anthracene, phenanthrene, indene, etc. A condensed ring may be formed.

R ^{45 to} R ⁴⁸ include hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group. Group, phosphonato group, amino group, ammonio group, methyl group, ethyl group, propyl group and other alkyl groups having 1 to 20 carbon atoms; cyclopentyl group, cyclohexyl group and other cycloalkyl groups having 4 to 23 carbon atoms; cyclopentenyl group A cycloalkenyl group having 4 to 23 carbon atoms such as cyclohexenyl group; an aryloxyalkyl group having 7 to 26 carbon atoms such as phenoxymethyl group, 2-phenoxyethyl group and 4-phenoxybutyl group (-ROAr group); benzyl An aralkyl group having 7 to 20 carbon atoms such as a 3-phenylpropyl group; An alkyl group having 2 to 21 carbon atoms having a cyano group such as a ruthenium group or β-cyanoethyl group; an alkyl group having 1 to 20 carbon atoms having a hydroxyl group such as a hydroxymethyl group, a methoxy group, an ethoxy group, or a benzyloxy group An alkyl ether group optionally substituted by an aryl group having 1 to 20 carbon atoms; an aryl ether group such as a phenoxy group or a naphthyloxy group; an alkylthio group having 1 to 20 carbon atoms such as a methylthio group or an ethylthio group (-SR Group); arylthioether groups such as benzylthio group and naphthylthio group; amide groups having 2 to 21 carbon atoms such as acetamido group and benzenesulfonamide group (C ₆ H ₅ SO ₂ NH ₂ —); acetyl group, benzoyl group and the like An acyl group having 1 to 20 carbon atoms; a thioacyl group; an acylthio group such as an acetylthio group or a benzoylthio group; Group, acetoxy group, benzyloxycarbonyl group, etc., C2-C21 ester group (-COOR group and -OCOR group), and C6-C20 substituted by electron-donating group and / or electron-withdrawing group Benzyl group, cyano group; carbamoyl group; carbamoyloxy group; cyanooxy group (cyanato group); cyanothio group (thiocyanato group); formyl group Is preferred. The alkyl moiety may be linear, branched or cyclic.
In addition, as R ^{45 to} R ⁴⁸ , two or more of them are bonded to each other and a condensed ring such as naphthalene, anthracene, phenanthrene, and indene is shared by sharing the atoms of the benzene ring to which R ^{45 to} R ⁴⁸ are bonded. Even if it forms, it is preferable from the point which absorption wavelength becomes long.

In formula (7), R ⁴⁹ is a hydrogen atom or a protecting group that can be deprotected by heating and / or irradiation with electromagnetic waves. Here, “deprotectable” means that there is a possibility of changing from —OR ⁴⁹ to —OH. When R ⁴⁹ is a hydrogen atom, the base generator according to the present invention loses the phenolic hydroxyl group by cyclization to change the solubility, and in the case of a basic aqueous solution, the solubility decreases. To do. Thereby, when the polymer precursor contained in the photosensitive resin composition according to the present invention, which will be described later, is a polyimide precursor or a polybenzoxazole precursor, the solubility decreases due to the reaction of the precursor to the final product. It is possible to increase the solubility contrast between the exposed area and the unexposed area.

Further, when R ⁴⁹ is a protective group that can be deprotected by heating and / or irradiation with electromagnetic waves, it is deprotected by heating and / or irradiation with electromagnetic waves to generate a hydroxyl group. By protecting the phenolic hydroxyl group with a protecting group that can be deprotected by heating and / or irradiation with electromagnetic waves, the compatibility with the compound to be combined, for example, the polymer precursor is improved by appropriately selecting the protecting group, The range of compounds that can be combined is increased. For example, a polymer precursor that is not preferably coexisting with a phenolic hydroxyl group can be used in the resin composition. R ⁴⁹ may be a protecting group for a phenolic hydroxyl group that can be deprotected by heating and / or irradiation with electromagnetic waves under conditions where the amide group present in formula (7) does not decompose in the base generator used in the present invention. As long as it is not particularly limited, it can be used. For example, an amide bond is a strong acid such as boron tribromide or aluminum trichloride, a strong Lewis acid such as sulfuric acid, hydrochloric acid or nitric acid, or a strong base such as sodium hydroxide. Decomposes on heating under basic conditions. Accordingly, such a protecting group that can be deprotected only by heating under strongly acidic or strongly basic conditions is inappropriate as a protecting group used in the base generator of the present invention. R ⁴⁹ is selected as appropriate depending on the type of compound used in combination with the base generator, the application method of the base generator, and the synthesis method for the purpose of improving solubility and compatibility or changing the reactivity during synthesis. It is what is done.

R ⁴⁹ can be selected from a silyl group, a silanol group, a phosphino group, a phosphinyl group, a phosphono group, or an organic group. The organic group for R ⁴⁹ is usually a monovalent organic group.

  Although the specific example of Formula (7) is given below, it is not limited to this.

  Moreover, as a photobase generator used by this invention, the compound shown to following General formula (8) is mentioned, for example.

(In Formula (8), R ⁴¹ and R ⁴² each independently represent a hydrogen atom or an organic group, and may be the same or different. R ⁴¹ and R ⁴² are bonded to form a ring. may form a structure, may contain a binding heteroatom. proviso that at least one of R ⁴¹ and R ⁴² is an organic group .R ⁵⁰ and R ^{50 'each} independently represents a hydrogen atom, A halogen atom, a hydroxyl group, a mercapto group, a nitro group, a silyl group, a silanol group, or an organic group, R ⁵¹ , R ⁵² , R ⁵³ , R ^54, and R ⁵⁵ are each independently a hydrogen atom, a halogen atom, or a hydroxyl group; , Mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group Amino group, an ammonio group or an organic group, may be different even in the same ^{.R 51, R 52, R 53} , R 54 and ^{R 55} are a ring structure bonded to two or more of them It may be formed or may contain a heteroatom bond.)

When the base generator represented by the chemical formula (8) is irradiated with electromagnetic waves, the bond is cleaved by the photodecarboxylation reaction of the carbamate bond to generate a base (NHR ¹ R ² ).

In the chemical formula (8), R ⁴¹ and R ⁴² may be the same as those described in the chemical formula (7).

In the chemical formula (8), R ⁵⁰ and R ^{50 ′} are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a silyl group, a silanol group, or an organic group. The same as those mentioned in R ^{51 to} R ⁵⁵ described later can be used.

R ^{51 to} R ^{55 in} the chemical formula (8) are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate. Group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group or organic group, which may be the same or different. Two or more of R ^{51 to} R ⁵⁵ may be bonded to each other to form a cyclic structure, or may include a hetero atom bond.

It is preferable to introduce one or more substituents into R ^{51 to} R ⁵⁵ in the chemical formula (8). In R ^{51 to} R ⁵⁵ , the wavelength of light to be absorbed can be adjusted by introducing at least one substituent as described above, and a desired wavelength can be absorbed by introducing a substituent. It can also be. The absorption wavelength can be shifted to a longer wavelength by introducing a substituent that extends the conjugated chain of the aromatic ring. It is also possible to improve the solubility and compatibility with the polymer precursor to be combined. Thereby, it is possible to improve the sensitivity of the photosensitive resin composition in consideration of the absorption wavelength of the polymer precursor to be combined.

R ^{51 in the} chemical formula (8) is preferably a nitro group from the viewpoint of improving the sensitivity of the base generator represented by the chemical formula (8).

In R ^{51 to} R ⁵⁵ , examples of the halogen atom include fluorine, chlorine, bromine and the like.
In R ^{51 to} R ⁵⁵ , examples of the organic group include a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, an aryl group, an aralkyl group, and a saturated or unsaturated halogenated alkyl group. These organic groups may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group, and these may be linear, branched or cyclic. As the bond other than the hydrocarbon group in the organic group of R ^{51 to} R ⁵⁵ , the same bond as the bond other than the hydrocarbon group of R ⁴¹ and R ⁴² can be used. The organic group of R ⁵¹ to R ⁵⁵ may be bonded to the benzene ring via a bond other than a hydrocarbon group. In addition, in the organic groups of R ^{51 to} R ⁵⁵ , substituents other than hydrocarbon groups (substituents included in the organic groups, substituents different from hydrocarbon groups, and substituents that may be substituted with hydrocarbon groups) ) May be the same as the substituents other than the hydrocarbon groups of R ⁴¹ and R ⁴² .
The organic group is not particularly limited as long as the effect of the present invention is not impaired, and is a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, an aryl group, an aralkyl group, and a saturated or unsaturated halogenated alkyl group. , Cyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, carboxyl group, carboxylate group, acyl group, acyloxy group, hydroxyimino group, saturated or unsaturated Examples thereof include a saturated alkyl ether group, a saturated or unsaturated alkyl thioether group, an aryl ether group, and an aryl thioether group.
The organic group in R ^{51 to} R ⁵⁵ is usually a monovalent organic group, but may form a divalent or higher organic group in the case of forming a cyclic structure to be described later.

Moreover, two or more of R ^{51 to} R ⁵⁵ may be bonded to form a cyclic structure.
The cyclic structure is a combination of two or more selected from the group consisting of saturated or unsaturated alicyclic hydrocarbons, heterocycles, and condensed rings, and the alicyclic hydrocarbons, heterocycles, and condensed rings. The structure which becomes may be sufficient. For example, each of R ^{51 to} R ⁵⁵ may be a combination of two or more of them, and share a benzene ring atom to which each of R ^{51 to} R ⁵⁵ is bonded, such as naphthalene, anthracene, phenanthrene, indene, etc. A condensed ring may be formed.

R ^{51 to} R ⁵⁵ include hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group. Group, phosphonato group, amino group, ammonio group, methyl group, ethyl group, propyl group and other alkyl groups having 1 to 20 carbon atoms; cyclopentyl group, cyclohexyl group and other cycloalkyl groups having 4 to 23 carbon atoms; cyclopentenyl group A cycloalkenyl group having 4 to 23 carbon atoms such as cyclohexenyl group; an aryloxyalkyl group having 7 to 26 carbon atoms such as phenoxymethyl group, 2-phenoxyethyl group and 4-phenoxybutyl group (-ROAr group); benzyl An aralkyl group having 7 to 20 carbon atoms such as a 3-phenylpropyl group; An alkyl group having 2 to 21 carbon atoms having a cyano group such as a ruthenium group or β-cyanoethyl group; an alkyl group having 1 to 20 carbon atoms having a hydroxyl group such as a hydroxymethyl group, a methoxy group, an ethoxy group, a benzyloxy group, etc. An alkyl ether group which may be substituted with an aryl group having 1 to 20 carbon atoms; an aryl ether group such as a phenoxy group or a naphthyloxy group; an alkylthio group having 1 to 20 carbon atoms such as a methylthio group or an ethylthio group (- SR group); arylthioether groups such as benzylthio group and naphthylthio group; amide groups having 2 to 21 carbon atoms such as acetamido group and benzenesulfonamide group (C ₆ H ₅ SO ₂ NH ₂ —); acetyl group and benzoyl group An acyl group having 1 to 20 carbon atoms such as thioacyl group; an acylthio group such as acetylthio group and benzoylthio group; An ester group having 2 to 21 carbon atoms (-COOR group and -OCOR group), such as a ruthenium group, an acetoxy group, and a benzyloxycarbonyl group, and 6 to 6 carbon atoms substituted by an electron-donating group and / or an electron-withdrawing group Benzyl group, cyano group; carbamoyl group; carbamoyloxy group; cyanooxy group (cyanato group); cyanothio group (thiocyanato group); formyl group substituted by 20 aryl groups, electron donating group and / or electron withdrawing group It is preferable. The alkyl moiety may be linear, branched or cyclic.
In addition, as R ^{51 to} R ⁵⁵ , two or more of them are bonded to each other and a condensed ring such as naphthalene, anthracene, phenanthrene, and indene is shared by sharing the atoms of the benzene ring to which R ^{51 to} R ⁵⁵ are bonded. Even if it forms, it is preferable from the point which absorption wavelength becomes long.

  Although the specific example of Formula (8) is given below, it is not limited to this.

  Moreover, as a photobase generator used by this invention, the compound shown in following General formula (9) is mentioned, for example.

(In the formula (9), R ⁵⁷ is an amino group or an organic group substituted with an organic group, R ⁵⁸ and R ⁵⁹ are each independently a hydrogen atom, a halogen atom, a sulfide group, a silyl group, a silanol group, a nitro group, Group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, amino group, ammonio group or organic group, which may be the same or different, ^At least one of ⁵⁸ and R ^{59 is} an aromatic compound which may have a hetero atom, and two or more of R ⁵⁷ , R ⁵⁸ and R ⁵⁹ are bonded to form a cyclic structure. And may contain heteroatom bonds.)

  The base generator represented by the chemical formula (9) is an oxime ester derivative, which undergoes an intramolecular cleavage reaction by absorption of electromagnetic waves according to the following reaction formula to generate amine or hydrazine.

In the chemical formula (9), R ⁵⁷ is an amino group or an organic group substituted with an organic group. When R ^{57 in the} chemical formula (9) is an amino group substituted with an organic group, it has a carbamoyloxime structure represented by the following formula (9 ′), and generates an amine and hydrazine as described above. obtain.

(Wherein (9 ^{'), R 58} and ^{and R 59} is the same as the chemical formula ^{(9), R 71} and ^{R 72} are the same as ^{R 41} and ^{R 42} of Formula (7) ^{.R 58,} R ⁵⁹ , R ^71, and R ⁷² may be bonded to each other to form a cyclic structure, or may include a hetero atom bond.)

In the above chemical formulas (9) and (9 ′), at least one of R ⁵⁸ and R ^{59 is} an aromatic compound which may have a hetero atom. The state in which at least one of R ⁵⁸ and R ⁵⁹ is substituted with an aromatic compound refers to a state in which the aromatic compound is directly covalently bonded to the carbon to which R ⁵⁸ and R ⁵⁹ are bonded. say. Here, the aromatic compound is a cyclic unsaturated organic compound, and includes aromatic hydrocarbons and aromatic heterocyclic compounds. Examples of the aromatic compound include a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorene group, an anthranyl group, a phenanthrenyl group, and a pyrenyl group, as well as a furanyl group, a thiophenyl group, and a pyrrolyl group. And heteroaromatic compounds such as (thio) xanthenyl group, (thio) xanthonyl group, coumaryl group, anthraquinolyl group, and the like. The substituent that they may have may be the same as R ^{45 to} R ⁴⁸ described above. When one of R ⁵⁸ and R ⁵⁹ is an organic group other than an aromatic compound, it may be the same as R ^{45 to} R ⁴⁸ described above.

In the above chemical formulas (9) and (9 ′), R ⁵⁸ , R ⁵⁹ , R ^71, and R ⁷² may be bonded to form a cyclic structure by combining two or more of them. It may be included. Examples of the case where R ⁵⁸ and R ⁵⁹ are bonded to form a cyclic structure include an embodiment in which a fluorene ring is formed together with the carbon to which R ⁵⁸ and R ⁵⁹ are bonded. In addition, when R ⁵⁸ and R ⁵⁷ or R ⁵⁸ and R ⁷¹ are combined to form a cyclic structure, for example, R ⁵⁸ and R ⁵⁷ or R ⁵⁸ and R ⁷¹ are connected by an aliphatic hydrocarbon group. The aspect which is mentioned is mentioned.

  As a specific example of Formula (9), the compound shown by a following formula can be mentioned, for example.

  Specific examples of the formula (9 ′) include compounds represented by the following formulas.

As the photobase generator used in the present invention, photobase generators represented by Formula 7, Formula 8, and Formula 9 are preferable from the viewpoint of heat resistance and sensitivity, and the light described in Formula 7 is particularly preferable from the viewpoint of sensitivity. Base generators are preferred.
Next, the amine generated from the photobase generator will be described.

  The photobase generator used in the present invention is used in combination with the aforementioned polyimide precursor. Since the polyimide precursor has strong absorption in a wavelength region of less than 350 nm, it is desirable that the photobase generator has sensitivity in a wavelength region of 350 nm or more. In order to sufficiently exhibit the function of generating a base for the polyimide component to become a final product, it is necessary to have absorption for at least a part of the exposure wavelength. The wavelength of a high-pressure mercury lamp that is a general exposure light source includes 365 nm, 405 nm, and 436 nm. For this reason, it is preferable that the base generator in the present invention absorbs electromagnetic waves having at least one wavelength among electromagnetic waves having wavelengths of at least 365 nm, 405 nm, and 436 nm. In such a case, it is preferable because the number of applicable polyimide components is further increased.

  Examples of the basic substance generated in the photobase generator used in the present invention include amines represented by the following formula (A) and amidines represented by the following formula (B).

(R ^C each independently represents a hydrogen atom or a monovalent organic group, and may be the same or different. R ^C may combine to form a cyclic structure, It may contain a heteroatom bond, provided that at least one of R ^C is a monovalent organic group, and each R ^d is independently a hydrogen atom or a monovalent organic group, and the same R ^d may be bonded to each other to form a cyclic structure or may contain a hetero atom bond.)

In addition, when R ^C of the formula (A) has an amidine structure as contained in the formula (B), the generated base is not the amine of the formula (A) but the formula (B ) Belonging to amidine.

  In view of the large effect of the generated basic substance such as the catalytic effect as described above, it is preferable that the generated basic substance is an aliphatic amine or amidine because it is a highly basic amine. Among these, from the viewpoint of basicity, secondary or tertiary aliphatic amines or amidines are preferable. However, even when an aliphatic primary amine is used, a sufficient catalytic effect can be obtained as compared with the case where an aromatic amine is used. Therefore, among aliphatic amines, from the viewpoints of thermal properties such as 5% weight loss temperature, 50% weight loss temperature, thermal decomposition temperature, other physical properties such as solubility, ease of synthesis and cost, etc. It is desirable to appropriately select amidine.

In the present invention, the aliphatic amine is generated to achieve high sensitivity, and further, from the viewpoint of increasing the solubility contrast of the unexposed area of the exposed portion, directly with the nitrogen atom of R ^c in the formula (A). It is preferable that all bonded atoms are hydrogen atoms or carbon atoms having SP3 orbital (except when all of R ^c are hydrogen atoms).
Examples of the substituent in which the atom directly bonded to the nitrogen atom is a carbon atom having an SP3 orbital include a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, and a cyclic aliphatic hydrocarbon. An aliphatic hydrocarbon group composed of a group or a combination thereof. In addition, the said aliphatic hydrocarbon group may have substituents, such as an aromatic group, or may contain bonds other than hydrocarbons, such as a hetero atom, in a hydrocarbon chain. Preferable examples include a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, a phenoxyalkyl group having 7 to 26 carbon atoms, and an aryl having 7 to 26 carbon atoms. An alkyl group and a C1-C20 hydroxyalkyl group are mentioned.
Here, when R ^c has the above cyclic aliphatic hydrocarbon group or the above cycloalkyl group, a heterocyclic structure containing a nitrogen atom to which two of R ^c are linked to form a ring and R ^c is bonded Including the case of forming.

Specific examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, an ethynyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, a cyclohexyl group, an isobornyl group, a norbornyl group, and an adamantyl group. , A benzyl group and the like, but are not limited thereto.
Further, it becomes annularly two of R ^c linked, the heterocyclic structure when forming a heterocyclic structure containing a nitrogen atom to which R ^c is attached, for example, aziridine (three-membered ring) Azetidine (4-membered ring), pyrrolidine (5-membered ring), piperidine (6-membered ring), azepane (7-membered ring), azocane (8-membered ring) and the like. These heterocyclic structures may have a substituent such as a linear or branched alkyl group. For example, as an alkyl substituent, a monoalkylaziridine such as methylaziridine, a dialkylaziridine such as dimethylaziridine, and methylazetidine Monoalkyl azetidine such as dialkyl azetidine such as dimethyl azetidine, trialkyl azetidine such as trimethyl azetidine, monoalkyl pyrrolidine such as methyl pyrrolidine, dialkyl pyrrolidine such as dimethyl pyrrolidine, trialkyl pyrrolidine such as trimethyl pyrrolidine, tetra Tetraalkylpyrrolidines such as methylpyrrolidine, monoalkylpiperidines such as methylpiperidine, dialkylpiperidines such as dimethylpiperidine, and trialkylpiperidines such as trimethylpiperidine Lysine, a tetraalkyl piperidine, such as tetramethylpiperidine, penta-alkyl piperidines such as such as pentamethyl piperidine.

In the present invention, the bond other than the hydrocarbon atom group in the organic group of R ^c is not particularly limited as long as the effect of the present invention is not impaired, and an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, Ester bond, amide bond, urethane bond, imino bond (-N = C (-R)-, -C (= NR)-, where R is a hydrogen atom or a monovalent organic group), carbonate bond, sulfonyl bond, Examples thereof include a sulfinyl bond and an azo bond. From the viewpoint of heat resistance, the bond other than the hydrocarbon atom group in the organic group includes an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, and an imino bond (—N═C ( -R)-, -C (= NR)-: where R is a hydrogen atom or a monovalent organic group), a carbonate bond, a sulfonyl bond, or a sulfinyl bond.

In the present invention, the substituent other than the hydrocarbon atom group in the organic group of R ^c is not particularly limited as long as the effect of the present invention is not impaired, and is a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group. Group, isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, Acyl group, acyloxy group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, hydroxyimino group, saturated or unsaturated alkyl ether group, saturated or unsaturated alkyl thioether group, aryl ether group And arylthioates Ter group, amino group (-NH2, -NHR, -NRR ': where R and R' are each independently a hydrocarbon atom group). The hydrogen atom contained in the substituent may be substituted with a hydrocarbon atom group. Moreover, the hydrocarbon atom group contained in the substituent may be linear, branched, or cyclic.

  Specific examples of amines generated during the decomposition of the photobase generator according to the present invention include primary amines such as n-butylamine, amylamine, hexylamine, cyclohexylamine, octylamine, and benzylamine, diethylamine, and diamine. Linear secondary amines such as propylamine, diisopropylamine and dibutylamine, secondary amines such as aziridine, azetidine, pyrrolidine, piperidine, azepane and azocan and secondary amines such as these alkyl substituents , Aromatic tertiary amines such as dimethylaniline, trimethylamine, triethylamine, tripropylamine, tributylamine, triethylenediamine, 1,4-diazabicyclo [2.2.2] octane, quinuclidine and 3-quinuclidinol Tribe Tertiary amines, and isoquinoline, pyridine, collidine, and heterocyclic tertiary amines such as beta-picoline and the like.

  Specific examples of the amidine generated upon decomposition of the photobase generator used in the present invention include secondary amidines such as imidazole, purine, triazole, guanidine, and derivatives thereof, pyrimidine, triazine, 1,8-diazabicyclo [ Tertiary amidine such as 5.4.0] undec-7-ene (DBU) and 1,5-diazabicyclo [4.3.0] non-5-ene (DBN), and derivatives thereof.

  In the present invention, among the above-mentioned photobase generators, those represented by the above formula (7) are preferable.

The base generator of the present invention can be synthesized by a plurality of conventionally known synthesis routes. The base generator represented by the chemical formula (7) can be synthesized with reference to Japanese Patent Application No. 2010-176384, for example. In the base generator represented by the chemical formula (7), the protecting group (R ⁴⁹ ) in the phenolic hydroxyl group may be introduced during the synthesis or may be introduced at the end of the synthesis. The base generator represented by the chemical formula (8) can be synthesized with reference to, for example, Japanese Patent Application Laid-Open Nos. 2006-189591 and 2008-247747. The base generator represented by the chemical formula (9) can be synthesized with reference to, for example, Japanese Patent Application Laid-Open Nos. 2007-249013 and 2008-003581.

1-3. Solvent The solvent used in the present invention is not particularly limited as long as it can uniformly disperse or dissolve the polyimide component and the photosensitive component. For example, diethyl ether, tetrahydrofuran, dioxane, ethylene glycol Ethers such as dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether Glycol monoethers (so-called cellosolves); methyl ethyl ketone Of ketones such as ethyl acetate, butyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, and glycol monoethers. Esters such as acetates (eg methyl cellosolve acetate, ethyl cellosolve acetate), methoxypropyl acetate, ethoxypropyl acetate, dimethyl oxalate, methyl lactate, ethyl lactate; ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol Alcohols such as glycerin; methylene chloride, 1,1-dichloroethane, 1,2-dichloroethylene, 1-chloropropane, 1-chlorobutane, 1-chloropentane, Halogenated hydrocarbons such as lobenzene, bromobenzene, o-dichlorobenzene, m-dichlorobenzene; N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, etc. Amides; pyrrolidones such as N-methylpyrrolidone; lactones such as γ-butyrolactone; sulfoxides such as dimethyl sulfoxide; other organic polar solvents; and further aromatics such as benzene, toluene and xylene. Group hydrocarbons and other organic nonpolar solvents are also included. These solvents are used alone or in combination of two or more.
Among them, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, dimethyl sulfoxide, hexa Polar solvents such as methylphosphoamide, N-acetyl-2-pyrrolidone, pyridine, dimethyl sulfone, tetramethylene sulfone, dimethyltetramethylene sulfone, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone It is mentioned as a suitable thing.

1-4. Other components Although the photosensitive resin composition in this invention contains the said polyimide precursor and a photobase generator at least, it may contain the other component as needed.
As such other components, a thermosetting component, a non-polymerizable binder resin other than the polyimide precursor, and other additives may be blended to prepare a low outgas photosensitive polyimide resin composition.

  In the present invention, various organic or inorganic low-molecular or high-molecular compounds may be blended in addition to impart processing characteristics and various functionalities to the photosensitive resin composition. For example, dyes, surfactants, leveling agents, plasticizers, fine particles and the like can be used. The fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, inorganic fine particles such as colloidal silica, carbon, and layered silicate, and these may have a porous or hollow structure. The function or form includes pigments, fillers, fibers, and the like.

  Moreover, the blending ratio of the other optional components in the present invention is preferably in the range of 0.1 wt% to 20 wt% with respect to the entire solid content of the photosensitive resin composition. If it is less than 0.1% by weight, the effect of adding the additive is difficult to be exhibited, and if it exceeds 20% by weight, the properties of the finally obtained resin cured product are hardly reflected in the final product.

2. Method for Forming Relief Pattern The photosensitive resin composition according to the present invention is suitably used as a pattern forming material.
The method for forming a relief pattern of the present invention includes at least
(1) A step of forming a coating film or a molded body using a negative photosensitive resin composition,
(2) A step of irradiating the coating film or molded body with electromagnetic waves in a predetermined pattern,
(3) It has the process of heating the said coating film or a molded object after irradiation with electromagnetic waves or simultaneously with irradiation, and (4) the process of developing, and may have another process as needed. Is.
Hereinafter, each process will be described in order.

(1) The process of forming a coating film or a molded object using a photosensitive resin composition Forming a coating film by applying the negative photosensitive resin composition according to the present invention on a certain substrate, etc. A molded body is formed by a different molding method.
The method for applying is not particularly limited. For example, a method using a known printing technique such as a spin coating method, a die coating method, a dip coating method, a bar coating method, a gravure printing method, a screen printing method, a flexographic printing, or an inkjet method. Can be used.
Examples of the molding method include injection molding (injection molding), blow molding, sheet molding (vacuum molding / pneumatic molding), tube molding (extrusion molding), and the like, but are not particularly limited.

  Moreover, as a base material at the time of forming a coating film, although it does not specifically limit, a silicon wafer, a metal substrate, a ceramic substrate, a glass substrate, a resin-made board | substrate etc. can be mentioned.

  After the negative photosensitive resin composition is applied or molded, it can be dried, that is, heated to remove most of the solvent, thereby giving a non-adhesive coating or molded product on the substrate surface. Although there is no restriction | limiting in particular in the thickness of a coating film, It is preferable that the film thickness after drying is 0.5-50 micrometers, and it is more desirable that it is 1.0-20 micrometers from a sensitivity and a development speed surface. What is necessary is just to determine suitably as drying conditions of the apply | coated coating film according to the component of the said composition, a use ratio, the kind of organic solvent, etc. Usually, 30-250 degreeC, Preferably it is 50-200 degreeC, More preferably, it is 70-150. ° C. The pre-bake time is usually about 30 seconds to 60 minutes. Examples of the heating method include, but are not limited to, a hot plate, an oven, an infrared heating furnace, and a conveying hot air furnace.

(2) The process of irradiating the said coating film or a molded object with electromagnetic waves in a predetermined pattern shape The obtained coating film or molded object is irradiated with electromagnetic waves through a mask having a predetermined pattern to irradiate the electromagnetic waves in a pattern shape.

  The exposure method and exposure apparatus used in the exposure process of irradiating electromagnetic waves are not particularly limited, and may be contact exposure or indirect exposure, and a contact / proximity exposure machine using a g-line stepper, i-line stepper, or ultrahigh pressure mercury lamp, A mirror projection exposure machine or other projectors or radiation sources that can irradiate ultraviolet rays, visible rays, X-rays, electron beams, or the like can be used.

(3) Step of heating the coating film or molded body after irradiation with electromagnetic waves or simultaneously with irradiation When the coating film or molded body is heated after irradiation with electromagnetic waves or simultaneously with the winner, a basic substance is generated in the exposed area. And the thermosetting temperature of the part selectively falls. After the exposure or simultaneously with the exposure, the exposed portion is heat-cured but the unexposed portion is heated at a processing temperature that is not heat-cured to cure only the exposed portion. The heating step for generating the basic substance and the heating step (post-exposure bake) for performing the reaction for curing only the exposed portion may be the same step or different steps. As a heating method, a hot plate, an oven, an infrared heating furnace, a transporting hot air furnace, and the like can be raised, but not particularly limited.

  The heating temperature may be appropriately selected depending on the curable component in the negative photosensitive resin composition, but is 80 ° C to 300 ° C, preferably 120 ° C to 250 ° C, more preferably 135 ° C to 200 ° C. It is. When the heat treatment temperature is lower than 80 ° C., the efficiency of the curing reaction is poor, and it becomes difficult to cause a difference in the curing reaction rate between the exposed and unexposed areas. On the other hand, when the heat treatment temperature exceeds 350 ° C., the curing reaction may proceed even in the unexposed area, and it may be difficult to cause a difference in solubility between the exposed area and the unexposed area.

  The heating time may be appropriately selected depending on the film thickness and the curable component in the negative photosensitive resin composition, but is usually 30 seconds to 1 hour, preferably 1 minute to 30 minutes.

(4) Developing Step The developing solution used in the developing step is not particularly limited as long as the solvent that changes the solubility of the electromagnetic wave irradiation site is used as the developing solution, and a basic aqueous solution, an organic solvent, or the like is used. It is possible to select appropriately according to the molecular precursor.

Although it does not specifically limit as basic aqueous solution, For example, other than tetramethylammonium hydroxide (TMAH) aqueous solution whose density | concentration is 0.01 weight%-10 weight%, Preferably, 0.05 weight%-5 weight%. , Diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl Examples include aqueous solutions such as methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine, and tetramethylammonium, among which 0.05% to 5% by weight of tetramethylammonium hydroxy. (TMAH) aqueous solution, especially preferred because it can form a pattern stably.
The solute may be one type or two or more types, and may contain 50% or more of the total weight, more preferably 70% or more, and an organic solvent or the like as long as water is contained.

  The organic solvent is not particularly limited, but polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolaclone, dimethylacrylamide, methanol, Alcohols such as ethanol and isopropanol, esters such as ethyl acetate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone, other tetrahydrofuran, chloroform, acetonitrile and the like alone or Two or more types may be added in combination. After development, washing is performed with water or a poor solvent. Also in this case, alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water.

  Examples of the developing method include a spray method, a liquid piling method, a dipping method, and a rocking dipping method.

(5) Other steps After development, if necessary, rinse with water or a poor solvent and dry at 80 to 100 ° C. to stabilize the pattern.
Further, it is preferable to complete the thermosetting by further heating the pattern as necessary. In the case of the photosensitive resin composition of the present invention, the relief pattern may be heated at a temperature of 180 to 500 ° C., preferably 200 to 350 ° C. for several tens of minutes to several hours in order to make it heat resistant. preferable.

  The photosensitive resin composition or the cured product thereof according to the present invention is a resin such as printing ink, paint, sealant, adhesive, electronic material, optical circuit component, molding material, resist material, building material, stereolithography, optical member, etc. It can be used in all known fields and products where the material is used. It can be suitably used both for applications that are used by exposing the entire surface, such as paints, sealants, and adhesives, and for applications that form patterns such as permanent films and release films.

  The photosensitive resin composition according to the present invention can be used in a wide range of fields, products such as heat resistance, dimensional stability, and insulation, such as paints, printing inks, sealants, or adhesives, or It is suitably used as a forming material for a display device, a semiconductor device, an electronic component, a micro electro mechanical system (MEMS), an optical member, or a building material. For example, specifically, as a forming material for an electronic component, a sealing material and a layer forming material can be used for a printed wiring board, an interlayer insulating film, a wiring covering film, and the like. Moreover, as a forming material of a display device, a layer forming material or an image forming material can be used for a color filter, a film for flexible display, a resist material, an alignment film, and the like. Further, as a material for forming a semiconductor device, a resist material, a layer forming material such as a buffer coat film, or the like can be used. Further, as a material for forming an optical component, it can be used as an optical material or a layer forming material for a hologram, an optical waveguide, an optical circuit, an optical circuit component, an antireflection film, or the like. Moreover, as a building material, it can use for a coating material, a coating agent, etc. It can also be used as a material for an optically shaped object. A printed matter, a paint, a sealant, an adhesive, a display device, a semiconductor device, an electronic component, a microelectromechanical system, an optically shaped article, an optical member, or a building material is provided.

  Since it has the above characteristics, the photosensitive resin composition according to the present invention can also be used as a pattern forming material. When the photosensitive resin composition according to the present invention is used as a pattern forming material (resist), the pattern formed thereby functions as a component that imparts heat resistance and insulation as a permanent film made of polyimide, for example, Suitable for forming color filters, flexible display films, electronic components, semiconductor devices, interlayer insulation films, wiring coating films, optical circuits, optical circuit components, antireflection films, and other optical or electronic members .

Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention.
[Production Example 1]
Preparation of polyimide precursor 1 solution (Synthesis of phthalic acid end-capped polyimide precursor)
Under a nitrogen stream, 2,1.7 '(0.568 mol) of 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (TFMB) and 2,2'-dimethyl-4,4'-diaminobiphenyl (mTBHG) ) 120.47 g (0.568 mol) was put into a 5000 ml separable flask, dissolved in 2999 g of dehydrated N-methyl-2-pyrrolidone (NMP), and the liquid temperature was 50 by a mantle heater under a nitrogen stream. The mixture was stirred with heating while monitoring with a thermocouple so that the temperature became 0 ° C. After confirming that they were completely dissolved, 324.15 g (97 mol% with respect to the total diamine) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) was added at 50 ° C. The mixture was stirred for 5 hours to obtain a polyimide precursor A. A small amount was sampled from this solution, reprecipitated with acetone, and dried under reduced pressure to take out polyimide precursor A from the solution. The amount of terminal groups of this polyimide precursor A was calculated by obtaining the degree of polymerization from the integral ratio of ¹ H-NMR spectrum. The amount of terminal groups is the ratio (mol%) of diamines present in the terminal groups in the total diamine added. As a result, the amount of terminal groups was 6.07 mol% (0.069 mol) based on the amount of diamine used in the reaction. Thereafter, 10.22 g (0.069 mol) of phthalic anhydride was added, and the mixture was stirred at 50 ° C. for 1 hour and end-capped. Thereafter, it was cooled to room temperature to obtain a polyimide precursor 1 solution whose ends were sealed with a substituent derived from phthalic anhydride. The number average molecular weight of the polyimide precursor 1 obtained from ¹ H-NMR is 18500, and the end capping ratio [number of terminal amino groups reacted with phthalic anhydride × 100 / (terminal reacted with phthalic anhydride] The number of amino groups in the above group + the number of unreacted terminal amino groups)] was 95% or more.

[Production Example 2]
Preparation of polyimide precursor 2 solution (synthesis of acid anhydride-terminated polyimide precursor)
A 5000 ml separable flask containing 334.23 g (1.136 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) and 2999 g of dehydrated N-methyl-2-pyrrolidone (NMP) Then, the mixture was stirred with heating while monitoring with a thermocouple so that the liquid temperature became 50 ° C. with a mantle heater under a nitrogen stream. Then, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl (TFMB) 176.29 g (0.551 mol) and 2,2′-dimethyl-4,4′-diaminobiphenyl (mTBHG) A powder mixed with 116.86 g (0.551 mol) was gradually added and stirred at 50 ° C. for 5 hours. Thereafter, the mixture was cooled to room temperature to obtain an acid anhydride-terminated polyimide precursor 2 solution. A small amount was sampled from this solution, reprecipitated with acetone, dried under reduced pressure, polyimide precursor 2 was taken out from the solution, the degree of polymerization was determined from the integral ratio of the ¹ H-NMR spectrum, and the number average molecular weight was calculated. ^The number average molecular weight determined from ¹ H-NMR was 18,800.

[Production Example 3]
Preparation of polyimide precursor 3 solution (phthalate end-capped polyimide precursor synthesis)
Under a nitrogen stream, 1238 g of dehydrated N-methyl-2-pyrrolidone (NMP) was put into a 2000 ml separable flask, and the mixture was stirred while heating by monitoring with a thermocouple so that the liquid temperature became 50 ° C. with an oil bath. 106.327 g (0.5310 mol) of 4,4′-diaminodiphenyl ether (ODA) was added. After confirming that they were completely dissolved, 152.679 g (98 mol% based on the total diamine) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) was added at 50 ° C. The mixture was stirred for 5 hours to obtain a polyimide precursor B. A small amount was sampled from this solution, reprecipitated with acetone, and dried under reduced pressure to take out polyimide precursor B from the solution. The terminal group amount of the polyimide precursor B was calculated in the same manner as in Production Example 1 from the integral ratio of ¹ H-NMR spectrum. As a result, the amount of terminal groups was 3.43 mol% (0.0182 mol) based on the amount of diamine used in the reaction. Thereafter, 2.664 g (0.0182 mol) of phthalic anhydride was added, and the mixture was stirred at 50 ° C. for 1 hour, and end-capped. Thereafter, the solution was cooled to room temperature to obtain a polyimide precursor 3 solution whose ends were sealed with a substituent derived from phthalic anhydride. The number average molecular weight of the polyimide precursor 3 determined from ¹ H-NMR was 27900, and the end capping rate was 85.3%.

[Production Example 4]
Preparation of polyimide precursor 4 solution (phthalic acid end-capped polyimide precursor synthesis)
85.54 g of dehydrated N-methyl-2-pyrrolidone (NMP) is charged into a 1000 ml separable flask under nitrogen flow, and is monitored and heated with a thermocouple so that the liquid temperature becomes 50 ° C. by an oil bath. While stirring. Charged 13.000 g (0.0435 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA), and then 1,3-bis (3-aminopropyl) tetramethyldisiloxane 5 .144 g (0.0207 mol) was charged. After confirming dissolution after 60 minutes, 401.68 g of dehydrated N-methyl-2-pyrrolidone (NMP) was added, and 37.305 g (0.1863 mol) of 4,4′-diaminodiphenyl ether (ODA) was dissolved. .
After confirming that they were completely dissolved, 46.660 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) (98 mol with respect to the total diamine in combination with BPDA charged earlier) %) Was added and stirred at 50 ° C. for 5 hours to obtain a polyimide precursor C. A small amount was sampled from this solution, reprecipitated with acetone, and dried under reduced pressure to take out the polyimide precursor C from the solution. The terminal group amount of the polyimide precursor C was calculated in the same manner as in Production Example 1 from the integral ratio of the ¹ H-NMR spectrum. As a result, the amount of terminal groups was 3.27 mol% (0.00609 mol) based on the amount of diamine used in the reaction. Thereafter, 0.9938 g (0.0182 mol) of phthalic anhydride was added, and the mixture was stirred at 50 ° C. for 1 hour, and end-capped. Thereafter, the solution was cooled to room temperature to obtain a polyimide precursor 4 solution whose ends were sealed with a substituent derived from phthalic anhydride. The number average molecular weight of the polyimide precursor 3 calculated | required from < ¹ > H-NMR was 29100, and the terminal blocking rate was 85.5%.

[Comparative Production Example 1]
Preparation of comparative polyimide precursor 1 solution (amine-terminated polyimide precursor synthesis)
Under a nitrogen stream, 2,1.7 '(0.568 mol) of 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (TFMB) and 2,2'-dimethyl-4,4'-diaminobiphenyl (mTBHG) ) 120.47 g (0.568 mol) was put into a 5000 ml separable flask, dissolved in 2999 g of dehydrated N-methyl-2-pyrrolidone (NMP), and the liquid temperature was 50 by a mantle heater under a nitrogen stream. The mixture was stirred with heating while monitoring with a thermocouple so that the temperature became 0 ° C. After confirming that they were completely dissolved, 324.15 g (97 mol% with respect to the total diamine) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) was added at 50 ° C. Stir for 5 hours. Thereafter, it was cooled to room temperature to obtain a comparative polyimide precursor 1 solution having an amino group terminal. A small amount was sampled from this solution, reprecipitated with acetone, dried under reduced pressure, the comparative polyimide precursor 1 was taken out of the solution, the degree of polymerization was determined from the integral ratio of the ¹ H-NMR spectrum, and the number average molecular weight was calculated. The number average molecular weight of the comparative polyimide precursor 1 obtained from ¹ H-NMR was 18100.

[Comparative Production Example 2]
Preparation of comparative polyimide precursor 2 solution (amine-terminated polyimide precursor synthesis)
Under a nitrogen stream, 1238 g of dehydrated N-methyl-2-pyrrolidone (NMP) was put into a 2000 ml separable flask, and the mixture was stirred while heating by monitoring with a thermocouple so that the liquid temperature became 50 ° C. with an oil bath. 106.327 g (0.5310 mol) of 4,4′-diaminodiphenyl ether (ODA) was added. After confirming that they were completely dissolved, 152.679 g (98 mol% based on the total diamine) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) was added at 50 ° C. Stir for 5 hours. Thereafter, the mixture was cooled to room temperature to obtain a comparative polyimide precursor 2 solution having an amino group terminal.
A small amount was sampled from this solution, reprecipitated with acetone, dried under reduced pressure, the polyimide precursor was taken out of the solution, the degree of polymerization was determined from the integral ratio of the ¹ H-NMR spectrum, and the number average molecular weight was calculated. The number average molecular weight of the comparative polyimide precursor 2 obtained from ¹ H-NMR was 27900.

[Comparative Production Example 3]
Preparation of comparative polyimide precursor 3 solution (synthesis of amine-terminated polyimide precursor)
85.54 g of dehydrated N-methyl-2-pyrrolidone (NMP) is charged into a 1000 ml separable flask under nitrogen flow, and is monitored and heated with a thermocouple so that the liquid temperature becomes 50 ° C. by an oil bath. While stirring. Charged 13.000 g (0.0435 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA), and then 1,3-bis (3-aminopropyl) tetramethyldisiloxane 5 .144 g (0.0207 mol) was charged. After confirming dissolution after 60 minutes, 401.68 g of dehydrated N-methyl-2-pyrrolidone (NMP) was added, and 37.305 g (0.1863 mol) of 4,4′-diaminodiphenyl ether (ODA) was dissolved. .
After confirming that they were completely dissolved, 46.660 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) (98 mol with respect to the total diamine in combination with BPDA charged earlier) %) Was added and stirred at 50 ° C. for 5 hours. Thereafter, the mixture was cooled to room temperature to obtain a comparative polyimide precursor 3 solution having an amino group terminal.
A small amount was sampled from this solution, reprecipitated with acetone, dried under reduced pressure, the polyimide precursor was taken out of the solution, the degree of polymerization was determined from the integral ratio of the ¹ H-NMR spectrum, and the number average molecular weight was calculated. The number average molecular weight of the comparative polyimide precursor 3 obtained from ¹ H-NMR was 29100.

<Dissolution rate evaluation 1>
Each of the polyimide precursors 1 and 2 obtained in Production Examples 1 and 2 and the comparative polyimide precursor 1 solution obtained in Comparative Production Example 1 were each dried on chrome-plated glass (50 mm × 50 mm). It spin-coated so that it might become a post-film thickness of 14 micrometers, and it was made to dry for 15 minutes on a 100 degreeC hotplate, and the coating film of Test example 1, 2 and the comparative test example 1 was produced. Then, each coating film was heated for 10 minutes on a 170 degreeC hotplate, and the dissolution rate evaluation sample was obtained.
About the obtained dissolution rate evaluation sample, the dissolution rate of the coating film at the time of developing using the aqueous solution which mixed 2.5 weight% of tetramethylammonium hydroxide and 20 weight% of isopropanol was measured. The results are shown below.
The dissolution rate is a value obtained by dividing the amount of film loss by the time of development processing. The amount of film reduction is the difference between the film thickness measured after developing with a developer for a certain period of time as described above, rinsing with distilled water and drying, and the initial film thickness of the developability evaluation sample. is there.

Dissolution rate of each sample Polyimide precursor 1 (Test Example 1): 61.6 nm / sec
Polyimide precursor 2 (Test Example 2): 67.2 nm / sec
Comparative polyimide precursor 1 (Comparative Test Example 1): 18.7 nm / sec

  Compared with the comparative polyimide precursor 1 of Comparative Test Example 1, the polyimide precursors 1 and 2 of Test Examples 1 and 2 improved the dissolution rate in an alkaline developer by about 3 times.

<Dissolution rate evaluation 2>
The polyimide precursor solution 3 solution obtained in Production Example 3 and the comparative polyimide precursor solution 2 solution obtained in Comparative Production Example 2 were dried on chrome-plated glass (50 mm × 50 mm), respectively, and the film thickness was 2 μm. And then dried on a hot plate at 120 ° C. for 15 minutes to prepare coating films of Test Example 3 and Comparative Test Example 2, respectively. Thereafter, each coating film was heated on a hot plate at 150 ° C. for 10 minutes to obtain a dissolution rate evaluation sample.
About the obtained dissolution rate evaluation sample, the dissolution rate of the coating film at the time of developing using the 2.38 weight% aqueous solution of tetramethylammonium hydroxide was measured. The results are shown below.
The dissolution rate is a value obtained by dividing the amount of film loss by the time of development processing. The amount of film reduction is the difference between the film thickness measured after developing with a developer for a certain period of time as described above, rinsing with distilled water and drying, and the initial film thickness of the developability evaluation sample. is there.

Dissolution rate of each sample Polyimide precursor 3 (Test Example 3): 200 nm / sec or more Comparative polyimide precursor 2 (Comparative Test Example 2): 55.2 nm / sec

The polyimide precursor 3 of Test Example 3 was too fast to calculate an accurate value. However, since the 2 μm coating film dissolved within at least 10 seconds, the dissolution rate was 200 nm / sec or more. Indicated.
Compared to the comparative polyimide precursor 2 of Comparative Test Example 2, the polyimide precursor 3 of Test Example 3 has an improved dissolution rate in an alkaline developer.

<Dissolution rate evaluation 3>
The polyimide precursor solution 4 solution obtained in Production Example 4 and the comparative polyimide precursor solution 3 solution obtained in Comparative Production Example 3 were dried on chrome-plated glass (50 mm × 50 mm), respectively, and the film thickness was 2 μm. And then dried on a hot plate at 120 ° C. for 15 minutes to prepare coating films of Test Example 3 and Comparative Test Example 2, respectively. Thereafter, each coating film was heated on a hot plate at 160 ° C. for 2 minutes to obtain a dissolution rate evaluation sample.
About the obtained dissolution rate evaluation sample, the dissolution rate of the coating film at the time of developing using the 2.38 weight% aqueous solution of tetramethylammonium hydroxide was measured. The results are shown below.

Dissolution rate of each sample Polyimide precursor 4 (Test Example 4): 200 nm / sec or more Comparative polyimide precursor 3 (Comparative Test Example 3): 111 nm / sec

The polyimide precursor 4 of Test Example 4 was too fast to calculate an accurate value, but since the 2 μm coating film dissolved within at least 10 seconds, the dissolution rate was 200 nm / sec or more. Indicated.
Compared with the comparative polyimide precursor 3 of the comparative test example 3, the polyimide precursor 4 of the test example 4 improved the dissolution rate with respect to the alkaline developer.

[Synthesis Example 1: Synthesis of photobase generator 1]
In a 100 mL flask, 2.00 g of potassium carbonate was added to 15 mL of methanol. In a 50 mL flask, 2.67 g (6.2 mmol) of ethoxycarbonylmethyl (triphenyl) phosphonium bromide and 945 mg (6.2 mmol) of 2-hydroxy-4-methoxybenzaldehyde are dissolved in 10 mL of methanol and added to a well-stirred potassium carbonate solution. Slowly dripped. After stirring for 3 hours, the completion of the reaction was confirmed by TLC, followed by filtration to remove potassium carbonate and concentration under reduced pressure. After concentration, 50 mL of 1N aqueous sodium hydroxide solution was added and stirred for 1 hour. After completion of the reaction, triphenylphosphine oxide was removed by filtration, and then concentrated hydrochloric acid was added dropwise to acidify the reaction solution. The precipitate was collected by filtration and washed with a small amount of chloroform to obtain 1.00 g of 2-hydroxy-4-methoxycinnamic acid. Subsequently, in a 100 mL three-necked flask, 500 mg (3.0 mmol) of 2-hydroxy-4-methoxycinnamic acid was dissolved in 40 mL of dehydrated tetrahydroxyfuran, and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride 0 .586 g (3.0 mmol) was added. After 30 minutes, 0.3 ml (3.0 mmol) of piperidine was added. After completion of the reaction, the reaction solution was concentrated and dissolved in water. After extraction with diethyl ether, the mixture was washed with saturated aqueous sodium hydrogen carbonate solution, 1N hydrochloric acid and saturated brine. Thereafter, 64 mg of a photobase generator 1 represented by the following formula was obtained by purification by silica gel column chromatography (developing solvent: chloroform / methanol 100/1 to 10/1).

[Synthesis Example 2: Synthesis of photobase generator 2]
Under a nitrogen atmosphere, 8.2 g (39 mmol) of 4,5-dimethoxy-2-nitrobenzaldehyde was dissolved in 100 mL of dehydrated 2-propanol in a 200 mL three-necked flask equipped with a Dean-Stark apparatus, and 2.0 g of aluminum isopropoxide ( 10 mmol, 0.25 eq.) Was added, and the mixture was heated and stirred at 105 ° C. for 7 hours. Along with the decrease in solvent evaporation, 40 mL of 2-propanol was added four times. After stopping the reaction with 150 mL of 0.2N hydrochloric acid, extraction was performed with chloroform, and the solvent was distilled off under reduced pressure to obtain 7.2 g of 6-nitroveratryl alcohol.
Under a nitrogen atmosphere, 5.3 g (25 mmol) of 6-nitroveratryl alcohol was dissolved in 100 mL of dehydrated dimethylacetamide in a 200 mL three-necked flask, and 7.0 mL (50 mmol, 2.0 eq) of triethylamine was added. In an ice bath, 5.5 g (27 mmol, 1.1 eq) of p-nitrophenyl chloroformate was added, and the mixture was stirred at room temperature for 16 hours. The reaction solution was poured into 2 L of water, the resulting precipitate was filtered, and purified by silica gel column chromatography to obtain 6.4 g of 4,5-dimethoxy-2-nitrobenzyl-p-nitrophenyl carbonate. .
Under a nitrogen atmosphere, 3.6 g (9.5 mmol) of 4,5-dimethoxy-2-nitrobenzyl-p-nitrophenyl carbonate was dissolved in 50 mL of dehydrated dimethylacetamide in a 100 mL three-necked flask, and 2,6-dimethylpiperidine 5 mL (37 mmol, 3.9 eq) and 1-hydroxybenzotriazole 0.36 g (0.3 eq) were added, and the mixture was heated and stirred at 90 ° C. for 18 hours. The reaction solution was poured into 1 L of 1% aqueous sodium hydrogen carbonate solution, and the resulting precipitate was filtered and washed with water to give a photobase generator 1N-{[(4,5-dimethoxy- There were obtained 2.7 g of 2-nitrobenzyl) oxy] carbonyl} -2,6-dimethylpiperidine.

[Example 1: Preparation of photosensitive resin composition A]
To the polyimide precursor 1 solution obtained in Production Example 1, 15% by weight of the photobase generator 1 was added to obtain a photosensitive resin composition A of Example 1.

[Example 2: Preparation of photosensitive resin composition B]
To the polyimide precursor 1 solution obtained in Production Example 1, 15% by weight of the photobase generator 2 was added to obtain a photosensitive resin composition B of Example 2.

[Example 3: Preparation of photosensitive resin composition C]
To the polyimide precursor 3 solution obtained in Production Example 3, 15% by weight of the photobase generator 1 was added to obtain a photosensitive resin composition C of Example 3.

[Example 4: Preparation of photosensitive resin composition D]
To the polyimide precursor 4 solution obtained in Production Example 4, 15% by weight of the photobase generator 1 was added to obtain a photosensitive resin composition D of Example 4.

[Comparative Example 1: Preparation of comparative photosensitive resin composition A]
To the comparative polyimide precursor 1 solution obtained in Comparative Production Example 1, 15% by weight of the photobase generator 1 was added to obtain a comparative photosensitive resin composition A of Comparative Example 1.

[Comparative Example 2: Preparation of comparative photosensitive resin composition B]
To the comparative polyimide precursor 1 solution obtained in Comparative Production Example 1, 15% by weight of the photobase generator 2 was added to obtain a comparative photosensitive resin composition B of Comparative Example 2.

[Comparative Example 3: Preparation of Comparative Photosensitive Resin Composition C]
To the comparative polyimide precursor 2 solution obtained in Comparative Production Example 2, 15% by weight of the photobase generator 1 was added to obtain a comparative photosensitive resin composition C of Comparative Example 3.

[Comparative Example 4: Preparation of Comparative Photosensitive Resin Composition D]
To the comparative polyimide precursor 3 solution obtained in Comparative Production Example 3, 15% by weight of the photobase generator 1 was added to obtain a comparative photosensitive resin composition D of Comparative Example 3.

<Developability evaluation 1>
Each of the photosensitive resin compositions A and B obtained in Examples 1 and 2 and the comparative photosensitive resin compositions A and B obtained in Comparative Examples 1 and 2 were each chromium-plated glass (50 mm × 50 mm). Then, each was spin-coated so as to have a thickness of 14 μm after drying, and dried on a hot plate at 100 ° C. for 15 minutes to prepare two coating films of the photosensitive resin composition. One of the coating films was used as a coating film for evaluating the exposed portion, and 5 J / cm ² exposure was performed with a high-pressure mercury lamp using a manual exposure machine. The remaining one was not exposed as a coating for evaluating the unexposed areas. Then, each coating film was heated using a conveyance type heating furnace so that the time in the zone of 170 ° C. was 5 minutes to obtain a developability evaluation sample. Each developability evaluation sample was used for evaluation as a set consisting of one coating film for evaluating the exposed area and one coating film for evaluating the unexposed area.
About the said set of the coating film of Examples 1-2 and Comparative Examples 1-2, it develops using the aqueous solution which mixed 2.5 weight% of tetramethylammonium hydroxide of 50 degreeC, and 20 weight% of isopropanol, respectively. The dissolution rate of the coating film was measured.
The dissolution rate was calculated from the amount of film reduction in the exposed and unexposed areas of each coating film, and a comparison was made. It can be evaluated that the higher the ratio of the dissolution rate of the coating film in the exposed area to the dissolution rate of the coating film in the unexposed area (solubility contrast), the higher the remaining film ratio.
The amount of film reduction is the difference between the film thickness measured after developing for a certain period of time using a developer as described above, rinsing with distilled water and drying, and the initial film thickness of the developability evaluation sample. The dissolution rate is a value obtained by dividing the film reduction amount by the development processing time.
The measurement results of each dissolution rate are shown in Tables 1 and 2.

As a result of the evaluation, when the photobase generator 1 was used, the photosensitive polyimide resin composition with the amine terminal sealed (Example 1) was compared with that without the amine terminal sealed (Comparative Example 1). The dissolution rate of the unexposed area was improved by about 5.5 times, and the time required for development could be shortened. Further, the solubility contrast between the exposed area and the unexposed area was improved about 3 times.
Further, from the results of Example 2 and Comparative Example 2, when the photobase generator 2 was used, the dissolution rate of the unexposed part was improved by about 1.3 times, and the solubility contrast of the exposed part and the unexposed part was about It was found to improve 2 times.

<Developability evaluation 2>
The photosensitive resin composition C obtained in Example 3 and the comparative photosensitive resin composition C obtained in Comparative Example 3 were each dried on chromium-plated glass (50 mm × 50 mm) so as to be 2 μm after drying. Each was spin-coated and dried on a hot plate at 120 ° C. for 15 minutes to prepare two coating films of the photosensitive polyimide resin composition. One of the coating films was used as a coating film for evaluating the exposed portion, and was exposed to 500 mJ / cm ^{2 with} a high-pressure mercury lamp using a manual exposure machine. The remaining one was not exposed as a coating for evaluating the unexposed area. Then, each coating film was heated for 10 minutes on a 150 degreeC hotplate, and the developability evaluation sample was obtained. In each developability evaluation sample, one coating film for evaluating the exposed portion and one coating film for evaluating the unexposed portion were used for evaluation as one set.
About the said set of the coating film of Example 3 and the comparative example 3, it developed by using the tetramethylammonium hydroxide 2.38 weight% aqueous solution, respectively, and measured the dissolution rate of the coating film.
The dissolution rate was calculated from the amount of film reduction in the exposed and unexposed areas of each coating film, and a comparison was made. It can be evaluated that the higher the ratio of the dissolution rate of the coating film in the exposed area to the dissolution rate of the coating film in the unexposed area (solubility contrast), the higher the remaining film ratio.
Table 3 shows the measurement results of the dissolution rates.

  As a result of the evaluation, the photosensitive polyimide resin composition (Example 3) in which the amine terminal is sealed is compared with the case where the photobase generator 1 is used as compared with the case where the photosensitive base resin agent 1 is not sealed (Comparative Example 3). The dissolution rate was improved about twice, and the time required for development could be shortened. In addition, the solubility contrast between the exposed area and the unexposed area was improved about twice.

<Developability evaluation 3>
The photosensitive resin composition C obtained in Example 3 and the comparative photosensitive resin composition C obtained in Comparative Example 3 were each dried on chromium-plated glass (50 mm × 50 mm) so as to be 2 μm after drying. Each was spin-coated and dried on a hot plate at 120 ° C. for 15 minutes to prepare two coating films of the photosensitive polyimide resin composition. One of the coating films was used as a coating film for evaluating the exposed portion, and was exposed to 500 mJ / cm ^{2 with} a high-pressure mercury lamp using a manual exposure machine. The remaining one was not exposed as a coating for evaluating the unexposed area. Then, each coating film was heated for 2 minutes on a 160 degreeC hotplate, and the developability evaluation sample was obtained. In each developability evaluation sample, one coating film for evaluating the exposed portion and one coating film for evaluating the unexposed portion were used for evaluation as one set.
About the said set of the coating film of Example 3 and the comparative example 3, it developed by using the tetramethylammonium hydroxide 2.38 weight% aqueous solution, respectively, and measured the dissolution rate of the coating film.
The dissolution rate was calculated from the amount of film reduction in the exposed and unexposed areas of each coating, and the comparison was made. It can be evaluated that the higher the ratio of the dissolution rate of the coating film in the exposed area to the dissolution rate of the coating film in the unexposed area (solubility contrast), the higher the remaining film ratio.
Table 4 shows the measurement results of the dissolution rates.

  As a result of the evaluation, the photosensitive polyimide resin composition (Example 3) in which the amine terminal is sealed is compared with the case where the end of the heat treatment (PEB) after exposure (PEB) is not sealed (Comparative Example 3). When the photobase generator 1 was used, the dissolution rate of the unexposed area was improved about twice, and the time required for development could be shortened. In addition, the solubility contrast between the exposed area and the unexposed area was improved about twice.

<Developability evaluation 4>
The photosensitive resin composition D obtained in Example 4 and the comparative photosensitive resin composition D obtained in Comparative Example 4 were each dried on chromium-plated glass (50 mm × 50 mm) so as to be 2 μm after drying. Each was spin-coated and dried on a hot plate at 120 ° C. for 15 minutes to prepare two coating films of the photosensitive polyimide resin composition. One of the coating films was used as a coating film for evaluating the exposed portion, and was exposed to 500 mJ / cm ^{2 with} a high-pressure mercury lamp using a manual exposure machine. The remaining one was not exposed as a coating for evaluating the unexposed area. Then, each coating film was heated for 2 minutes on a 160 degreeC hotplate, and the developability evaluation sample was obtained. In each developability evaluation sample, one coating film for evaluating the exposed portion and one coating film for evaluating the unexposed portion were used for evaluation as one set.
About the said set of the coating film of Example 4 and the comparative example 4, it developed, using the tetramethylammonium hydroxide 2.38 weight% aqueous solution, respectively, and measured the dissolution rate of the coating film.
The dissolution rate was calculated from the amount of film reduction in the exposed and unexposed areas of each coating film, and a comparison was made. It can be evaluated that the higher the ratio of the dissolution rate of the coating film in the exposed area to the dissolution rate of the coating film in the unexposed area (solubility contrast), the higher the remaining film ratio.
Table 5 shows the measurement results of each dissolution rate.

  As a result of the evaluation, the photosensitive polyimide resin composition (Example 4) in which the amine terminal is sealed is improved by about 4 times as much as the dissolution rate of the unexposed area compared to the case where the photosensitive polyimide resin composition (Example 4) is not sealed (Comparative Example 4). The time required for development could be shortened. Further, the solubility contrast between the exposed area and the unexposed area was improved about 3 times.

  As a result of the solubility contrast evaluation, Examples 1 to 4 using the polyimide precursor with the amine terminal sealed had a solubility contrast as compared with Comparative Examples 1 to 4 using the comparative polyimide precursor having an amine terminal. It was clear that it was suitable as a pattern forming material.

<Pattern formation evaluation 1>
The photosensitive resin composition A of Example 1 and the comparative photosensitive resin composition A of Comparative Example 1 were each spin-coated on chrome-plated glass (50 mm × 50 mm) so as to be 19 μm after drying, and 100 The coating was dried for 15 minutes on a hot plate at 0 ° C. to prepare a coating film of the photosensitive resin composition. This coating film was exposed to 200 mJ / cm ² through a photomask for thin line evaluation with a high-pressure mercury lamp using a manual exposure machine. Thereafter, the coating film was heated using a transport heating furnace so that the time in the zone of 170 ° C. was 2.5 minutes. The film thickness at that time was 13.9 μm in both Example 1 and Comparative Example 1. Subsequently, development processing was performed using an aqueous solution in which 2.5% by weight of tetramethylammonium hydroxide heated to 50 ° C. and 20% by weight of isopropanol were mixed to obtain a line and space (L / S) pattern.
Table 6 shows the development time, resolution (minimum L / S pattern that can be formed), post-development film thickness, and residual film ratio required to obtain the pattern.

<Pattern formation evaluation 2>
The photosensitive resin composition C obtained in Example 3 and the comparative photosensitive resin composition C obtained in Comparative Example 3 were each dried on chromium-plated glass (50 mm × 50 mm) so as to be 2 μm after drying. Each was spin-coated and dried on a hot plate at 120 ° C. for 15 minutes to prepare a coating film of the photosensitive resin composition. This coating film was exposed to 125 mJ / cm ² using a manual exposure machine with a high-pressure mercury lamp through a photomask for thin line evaluation. Thereafter, the coating film was heated on a hot plate at 160 ° C. for 2 minutes. The film thickness at that time was 1.7 μm in both Example 3 and Comparative Example 3. Subsequently, development processing was performed using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide.

As a result, the photosensitive resin composition of Example 3 had a development time of 120 seconds and a resolution (minimum value of L / S pattern that could be formed) of 6 μm / 6 μm, a post-development film thickness of 1.28 μm, and a residual film ratio of 75%. was gotten.
On the other hand, the photosensitive resin composition of Comparative Example 3 had a residual film of 0.18 μm remaining in the unexposed portion at a development time of 120 seconds, and a desired pattern could not be obtained.

  From the above, since the photosensitive resin composition of the present invention can shorten the development time, the process cost can be reduced, and the remaining film rate is high and a good pattern can be obtained.

That is, the photosensitive resin composition of the present invention contains at least a polyimide precursor containing a structure represented by the following formula (1) and a photobase generator photobase generator represented by the following formula (7). It is characterized by.

(In Formula (1), R ¹ is a tetravalent organic group, R ² is a divalent organic group, R ³ is a monovalent organic group having no hydrogen atom or amino group, R ⁴ is a hydrogen atom or the following formula: It is at least one organic group selected from the group consisting of organic groups represented by (2) to (5), and 50% or more of R ⁴ is represented by the formulas (2) to (5). A plurality of R ¹ , R ² , R ³ , and R ⁴ may be the same or different.)

(In formula (2), R ⁵ is a tetravalent organic group, and R ⁶ is a monovalent organic group having no hydrogen atom or amino group .)

(In Formula (3), R ⁷ is a tetravalent organic group, R ⁸ is a monovalent organic group having no hydrogen atom or amino group . Plural R ⁸ may be the same or different.)

(In formula (4), R ⁹ is a tetravalent organic group, R ¹⁰ is a monovalent organic group having no hydrogen atom or amino group , and R ¹¹ is a monovalent organic group having no hydrogen atom or amino group. A plurality of R ¹⁰ may be the same or different.)

(In the formula (5), X is a C, P or S atom, Y is an S or O atom, Z is —R ¹² or —OR ¹³ , and R ¹² and R ¹³ are monovalent organic compounds having no amino group. Group.)

(In formula (7), R ⁴¹ And R ⁴² Are each independently a hydrogen atom or an organic group, which may be the same or different. R ⁴¹ And R ⁴² May be bonded to each other to form a cyclic structure, or may contain a heteroatom bond. However, R ⁴¹ And R ⁴² At least one of these is an organic group. R ⁴³ And R ⁴⁴ Are independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group Group or organic group, which may be the same or different. R ⁴⁵ , R ⁴⁶ , R ⁴⁷ And R ⁴⁸ Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, A phosphonate group, an amino group, an ammonio group, or an organic group, which may be the same or different. R ⁴⁵ , R ⁴⁶ , R ⁴⁷ And R ⁴⁸ In these, two or more of them may be bonded to form a cyclic structure, and may contain a bond of a heteroatom. R ⁴⁹ Is a hydrogen atom or a protecting group that can be deprotected by heating and / or irradiation with electromagnetic waves. )

X in the formula (5) is a carbon atom, and Y in the formula (5) is an oxygen atom, it is easy to obtain an end-capping agent that forms such a terminal, and It is preferable because it is easy to handle.
Furthermore, when the formula (5) is an organic group represented by the following formula (6), when the polyimide precursor is imidized, the terminal site is also imidized, so that moisture is absorbed when it becomes a polyimide. This is preferable because the heat resistance is low and the heat resistance is high.

(In the formula (6), R ¹⁴ is an organic group selected from the group consisting of organic groups represented by the following formulas (6-1) to (6-5), and R ¹⁵ does not have a hydrogen atom or an amino group. Valent organic group.)

(In the formulas (6-1) to (6-5), A each independently represents an organic group having no hydrogen atom or amino group, and may be the same or different. Two or more of these may be bonded to form a cyclic structure, and may include a heteroatom bond.-COOR corresponds to -COOR ¹⁵ in formula (6).

[ Reference Example 2: Preparation of photosensitive resin composition B]
To the polyimide precursor 1 solution obtained in Production Example 1, 15% by weight of the photobase generator 2 was added to obtain a photosensitive resin composition B of Reference Example 2.

As a result of the evaluation, when the photobase generator 1 was used, the photosensitive polyimide resin composition with the amine terminal sealed (Example 1) was compared with that without the amine terminal sealed (Comparative Example 1). The dissolution rate of the unexposed area was improved by about 5.5 times, and the time required for development could be shortened. Further, the solubility contrast between the exposed area and the unexposed area was improved about 3 times.
Further, from the results of Reference Example 2 and Comparative Example 2, when the photobase generator 2 was used, the dissolution rate of the unexposed part was improved by about 1.3 times, and the solubility contrast of the exposed part and the unexposed part was about It was found to improve 2 times.

Claims (10)

A photosensitive resin composition containing at least a polyimide precursor having a structure represented by the following formula (1) and a photobase generator.
(In the formula (1), R ¹ is a tetravalent organic group, R ² is a divalent organic group, R ³ is a hydrogen atom or a monovalent organic group, R ⁴ is a hydrogen atom or the following formulas (2) to ( 5) is at least one organic group selected from the group consisting of organic groups, and at least a part of R ⁴ is an organic group, and a plurality of R ¹ , R ² , R ³ and R ⁴ are Each may be the same or different.)
(In Formula (2), R ⁵ is a tetravalent organic group, and R ⁶ is a hydrogen atom or a monovalent organic group.)
(In Formula (3), R ⁷ is a tetravalent organic group, R ⁸ is a hydrogen atom or a monovalent organic group. Plural R ^8s may be the same or different.)
(In Formula (4), R ⁹ is a tetravalent organic group, R ¹⁰ and R ¹¹ are a hydrogen atom or a monovalent organic group. Plural R ^10s may be the same or different.)
(In formula (5), X is a C, P or S atom, Y is an S or O atom, Z is —R ¹² or —OR ¹³ , and R ¹² and R ¹³ are monovalent organic groups.)   The photosensitive resin composition according to claim 1, wherein X in the formula (5) is a carbon atom, and Y in the formula (5) is an oxygen atom. Furthermore, the photosensitive resin composition of Claim 2 whose said Formula (5) is an organic group represented by following formula (6).
(In the formula (6), R ¹⁴ is an organic group selected from the group consisting of organic groups represented by the following formulas (6-1) to (6-5), and R ¹⁵ is a hydrogen atom or a monovalent organic group. is there.)
(In formulas (6-1) to (6-5), each A is independently hydrogen or an organic group, and may be the same or different. A is a combination of two or more of them. (It may form a cyclic structure and may contain a bond of a hetero atom. -COOR corresponds to -COOR ¹⁵ in the formula (6).) The photosensitive resin composition according to any one of claims 1 to 3, wherein 50% or more of R ⁴ in the formula (1) is an organic group. 5. The photosensitive resin composition according to claim 1, wherein 50% or more of R ⁴ in the formula (1) is an organic group represented by the formula (6).   The photosensitive resin composition according to any one of claims 1 to 5, wherein the photobase generator generates an aliphatic amine or amidine as a base. The photosensitive resin composition according to claim 1, wherein the photobase generator is at least one selected from the group consisting of compounds represented by the following formulas (7) to (9). object.
(In Formula (7), R ⁴¹ and R ⁴² each independently represent a hydrogen atom or an organic group, and may be the same or different. R ⁴¹ and R ⁴² are bonded to form a ring. It may form a structure and may contain a bond of hetero atoms, provided that at least one of R ⁴¹ and R ⁴² is an organic group, and R ⁴³ and R ⁴⁴ are each independently a hydrogen atom, A halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, or organic group, may be different even in the same ^{.R 45, R 46,} R ⁴⁷ and ^{R 48} are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, Sulf Group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group or organic group, which are the same. Two or more of R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ may be bonded to form a cyclic structure, and may contain a hetero atom bond. R ⁴⁹ is a hydrogen atom or a protecting group that can be deprotected by heating and / or irradiation with electromagnetic waves.)
(In Formula (8), R ⁴¹ and R ⁴² each independently represent a hydrogen atom or an organic group, and may be the same or different. R ⁴¹ and R ⁴² are bonded to form a ring. may form a structure, may contain a binding heteroatom. proviso that at least one of R ⁴¹ and R ⁴² is an organic group .R ⁵⁰ and R ^{50 'each} independently represents a hydrogen atom, A halogen atom, a hydroxyl group, a mercapto group, a nitro group, a silyl group, a silanol group, or an organic group, R ⁵¹ , R ⁵² , R ⁵³ , R ^54, and R ⁵⁵ are each independently a hydrogen atom, a halogen atom, or a hydroxyl group; , Mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group Amino group, an ammonio group or an organic group, may be different even in the same ^{.R 51, R 52, R 53} , R 54 and ^{R 55} are a ring structure bonded to two or more of them It may be formed or may contain a heteroatom bond.)
(In the formula (9), R ⁵⁷ is an amino group or an organic group substituted with an organic group, R ⁵⁸ and R ⁵⁹ are each independently a hydrogen atom, a halogen atom, a sulfide group, a silyl group, a silanol group, a nitro group, Group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, amino group, ammonio group or organic group, which may be the same or different, ^At least one of ⁵⁸ and R ^{59 is} an aromatic compound which may have a hetero atom, and two or more of R ⁵⁷ , R ⁵⁸ and R ⁵⁹ are bonded to form a cyclic structure. And may contain heteroatom bonds.)   The pattern formation material which consists of the photosensitive resin composition of any one of the said Claims 1 thru | or 7.   A coating film or a molded body is formed using the photosensitive resin composition according to any one of claims 1 to 7, and the coating film or the molded body is irradiated with an electromagnetic wave in a predetermined pattern. A negative pattern forming method characterized by heating after or simultaneously with irradiation to change the solubility of the irradiated portion and then developing.   Printed matter, paint, sealant, adhesive, display device, semiconductor device, electronic component, at least part of which is formed from the photosensitive resin composition according to any one of claims 1 to 7 or a cured product thereof. An article of any one of a micro electro mechanical system, an optically shaped object, an optical member, and a building material.